Oil-resistant composition

Abstract

To provide a solid oil-resistant agent composition capable of providing an oil-resistant agent aqueous dispersion when used.SOLUTION: An oil-resistant composition comprising a liquid-repellent compound, a dispersant, and an excipient, wherein the oil-resistant composition is solid.SELECTED DRAWING: None

Description

[Technical Field]

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

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

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-60921 Summary of the Invention [Problem to be solved by the invention]

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

[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: [Section 1] An oil-resistant composition comprising a liquid-repellent compound, a dispersant, and an excipient, the composition being solid. [Section 2] Item 2. The oil-resistant composition according to Item 1, wherein the liquid-repellent compound has a hydrocarbon group or a polysiloxane group having 6 to 40 carbon atoms. [Section 3] Item 3. The oil-resistant composition according to Item 1 or 2, wherein the liquid-repellent compound includes at least one selected from the group consisting of amine-modified compounds, polyol-modified compounds, polycarboxylic acid-modified compounds, and other solid oils. [Section 4] the liquid repellent compound is selected from the group consisting of an amine-modified compound, a polyol-modified compound, and a polycarboxylic acid-modified compound; The amine-modified compound is an amine skeleton, and The following formula: -Y N -Z N n [Y N is Y N1 and Y N2 is a (1+n) valent group consisting of one or more members selected from the group consisting of Y N1 is a group consisting 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' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms), 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, Z N represents a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group which may have a substituent, n is an integer between 1 and 3. and having one or more groups represented by At least one -Y N -Z N n is bonded to a nitrogen atom of the amine skeleton; The polyol modification may be achieved by modifying one or more hydroxy groups of the polyol to the formula: -Y O -ZO n [In the formula, Y O is Y O1 and Y O2 is a (1+n) valent group consisting of one or more members selected from the group consisting of Y O1 is a group consisting 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' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms), 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, Z O represents a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group which may have a substituent, n is an integer between 1 and 3. A compound substituted with a group represented by the formula: The polycarboxylic acid modification product is a polycarboxylic acid modified by converting a hydroxy group of one or more carboxyl groups of the polycarboxylic acid to the following formula: -Y C -Z C n [In the formula, Y C is Y C1 and Y C2 is a (1+n) valent group consisting of one or more members selected from the group consisting of Y C1 is a group consisting 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' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms), 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, Z C represents a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group which may have a substituent, n is an integer between 1 and 3. A compound substituted with a group represented by the formula: Item 4. The oil-resistant composition according to any one of Items 1 to 3. [Section 5] The amine skeleton is Ethylenediamine, propylenediamine, butylenediamine, pentanediamine, hexamethylenediamine; Diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine; 2-amino-1,3-propanediol; o-, m- or p-xylylenediamine; 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 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, and 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, isomaltodextrin, gellan gum, tamarind seed gum; Kojic acid, quinic acid, chlorogenic acid, gluconic acid; Glucosamine; Ascorbic acid, inositol; catechins, quercetin, anthocyanins; Glycerin, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, trimethylolpropane, trimethylolethane; 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; The polycarboxylic acid Citric acid, malic acid, glutaric acid, adipic acid, phthalic acid, alginic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, aldaric acid; Tricarballylic acid, t-aconitic acid, trimellitic acid; Pyromellitic acid; The following formula CH2=C(-Q)-C(=O)-OH [In the formula, Q is a hydrogen atom, a monovalent organic group, or a halogen atom other than a fluorine atom. a polymer containing a repeating unit derived from a compound represented by the formula: Item 5. The oil-resistant composition according to item 4, wherein the oil-resistant composition is at least one selected from the group consisting of benzophenone-3, benzophenone-4, benzophenone-5, benzophenone-6, benzophenone-7, benzophenone-8, benzophenone-9, benzophenone-10, benzophenone-11, benzophenone-12, benzophenone-13, benzophenone-14, benzophenone-1 [Section 6] Item 4. The oil-resistant composition according to Item 3, wherein the other solid oil comprises 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. [Section 7] Item 7. The oil-resistant agent 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, relative to 100 parts by weight of the liquid-repellent compound. [Section 8] 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. [Section 9] The excipient may be glucose, fructose, galactose, dextrin, sucrose, lactose, hydroxyethyl cellulose, hydroxypropyl cellulose, Item 9. The oil-resistant agent composition according to any one of Items 1 to 8, comprising at least one selected from the group consisting of methylcellulose, carboxymethylcellulose, 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, Agrobacterium sinoglycan, cationized guar gum, polyvinyl alcohol, polyacrylic acid, and sodium polyacrylate. [Section 10] Item 10. The oil-resistant agent 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. [Section 11] Item 11. The oil-proofing composition according to any one of Items 1 to 10, wherein the oil-proofing composition is in the form of a tablet, and the particle size thereof is 2,000 to 100,000 μm. [Section 12] Item 12. The oil-proofing composition according to any one of items 1 to 11, wherein the water content of the oil-proofing composition is 0.01% by weight to 20% by weight. [Section 13] Item 13. The oil-proofing agent 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. [Section 14] the liquid repellent compound is an amine-modified compound, The amine-modified compound 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 independently in each occurrence an alkyl group having from 14 to 24 carbon atoms; L 1 is independently in each occurrence a divalent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms; p, in each occurrence, is independently an integer between 1 and 2, inclusive; q is independently in each occurrence 0 or 1; p+q is each N(-C(=O)-Z N ) p (-H) q In, 2, r is independently in each occurrence 0 or 1; s is independently in each occurrence 0 or 1; r+s is each N(-C(=O)-Z N ) r (-H) s In, 1, t is an integer between 0 and 3. Item 14. The oil-proofing agent composition according to any one of items 1 to 13, wherein the compound is represented by the formula: [Section 15] Item 15. Grease-resistant paper comprising the liquid-repellent compound, dispersant, and excipient in the oil-proofing agent composition according to any one of Items 1 to 14. [Section 16] Item 16. Greaseproof paper according to item 15, which is a pulp molded product. [Section 17] mixing a liquid repellent compound, a dispersant, an excipient, and a liquid medium to obtain a precursor mixture; and The method for producing an oil-proofing composition includes subjecting the precursor mixture to a heat treatment or a drying treatment to obtain a solid oil-proofing composition. [Section 18] Item 18. A method for producing an oil-proofing composition according to Item 17, comprising tableting the oil-proofing composition. [Section 19] Item 15. 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; A method for producing a paper product, comprising treating paper with the aqueous dispersion by external or internal addition treatment. [Section 20] Item 15. 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; A method for producing a pulp mold, comprising filling a mold with the aqueous dispersion and a pulp base material, and allowing water to permeate out of the mold to form the pulp. [Effects of the Invention]

[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. DETAILED DESCRIPTION OF THE INVENTION

[0008] <Terminology> As used herein, an "n-valent group" refers to a group having n bonds, i.e., a group that forms n bonds. An "n-valent organic group" refers to an n-valent group containing carbon. Such organic groups are not particularly limited, but may be hydrocarbon groups or derivatives thereof. A hydrocarbon group derivative refers to a group having one or more 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 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-resistant 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-proofing agent, oil-proofing 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 by itself as the oil-proofing composition, 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 the performance (e.g., water resistance, oil resistance, paper strength, etc.) of paper products obtained from a pulp composition to which the oil-proofing composition has been added can be improved.

[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, and does not need to be stored 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-mentioned 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, where "powder" means an aggregate of particles with 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 more, 0.3% or more, 0.5% or more, 1% or more, 1.5% or more, 3% or more, 4% or more, 5% or more, or 10% or more. 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 less, 30% or less, 20% or less, 15% or less, 10% or less, 5% or less, 3% or less, or 1.5% or less. 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 of the water-dispersed composition obtained by redispersing the oil-proofing agent composition of the present disclosure in water, as measured by a laser diffraction scattering method, may be 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.25 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 agent 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 the form of a tablet, 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 the form of a tablet, 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 Over 20mm 3 Above, 30mm 3 Above 50mm 3 Above, 70mm 3 Over 100mm 3, 150mm 3 Over 200mm 3 More than 250mm 3 Over 300mm 3 Over 400mm 3 or more, or 500mm 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 of 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 properties that the liquid repellent compound may have are listed below. These properties 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, and 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 (especially oil repellency) to the substrate. The HD contact angle is the static contact angle of the liquid-repellent compound with 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, and 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 still 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', -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 an 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 ratio of carbon atoms to the total 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 ratio of carbon atoms to the total 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 (for example, 1) -OR' (particularly -OH) as a substituent (for example, other than at the terminal).

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

[0041] The polysiloxane group has the formula: -[-Si(R s )2-O-] a - [In the formula, R s is independently in each occurrence a hydrocarbon group or a reactive group having 1 to 40 carbon atoms; a is an integer between 5 and 10,000. It may be expressed as:

[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 hydrocarbon groups having 1 to 5 carbon atoms include hydrocarbon groups having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group (particularly aliphatic hydrocarbon groups, particularly alkyl groups 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., hydroxyl, amino, mercapto, epoxy, carboxyl, halogen-substituted alkyl, vinyl, (meth)acrylic, (meth)acryloyloxy, and (meth)acrylamide groups, and hydrogen atoms directly bonded to silicon atoms). These functional groups may be directly bonded to the silicon atom or 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 alkylene groups preferably have from 2 to 10 carbon atoms. Divalent aromatic groups preferably have from 6 to 12 carbon atoms. The reactive group may be a group selected from the group consisting of a hydroxyl 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 hydroxyl 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 quantity 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 is preferably 50 mol % or more, based on the total of R s The quantity of R s For example, the total amount of R s Based on 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 quantity 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 quantity 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, the reactive group R s The quantity 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 quantity 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, for example, -OR s , -Si(R s )3, etc. The R 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 -OL s1 -[-Si(R s )2-O-] a -R s -L s1 -[-Si(R s )2-O-] a -Si(R s )3 -L s1 -OL 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, R s 50 mol % or more of the total groups are methyl groups, L s1 is a hydrocarbon group having 1 to 20 carbon atoms, a is between 5 and 10,000. [ka] [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.] etc.

[0055] [Examples of liquid-repellent compounds] An example of the liquid-repellent compound is a compound having a hydrocarbon group with a carbon number of 6 to 40. Examples of the hydrocarbon group and the preferred range 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 contain 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 contain -C(=O)-O-, -OC(=O)-, -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'-, or -SONR'- (where R' 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 obtained by bonding a raw material compound and a modifying group (particularly the monovalent hydrocarbon group optionally having the above-mentioned substituent) 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 a broad amide structure and may be selected from 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 may be an amide structure selected from the group consisting of -(C=O)N(-)2, -(C=S)N(-)2, and -S(=O)2N(-)2 (note that each group may be inverted). Here, at least one of the bonds possessed by 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 amide groups, urethane groups, urea groups, and imide groups.

[0058] [Amount of liquid repellent compound] The amount of the liquid repellent compound in the oil-proofing composition may be 0.01% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, or 30% by weight or more. The amount of the liquid repellent compound in the oil-proofing composition may be 95% 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, 10% by weight or less, 5% by weight or less, or 3% by weight or less. The liquid repellent compound may be used alone as the oil-proofing composition.

[0059] [Amine-modified compounds] As an example of the 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-repellent properties.

[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 impurity components. On the other hand, amine-modified compounds can be made into low-molecular-weight compounds, narrowing (uniformizing) the molecular weight distribution, and can therefore have good 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, e.g., 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 about 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 of 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 refers to a group selected from the group consisting of -NH, -NH-, and -N(-) and includes amino groups adjacent to carbonyl groups contained in amide groups, urethane groups, urea groups, imides, etc. Note that the amine skeleton may be any 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 is one or more groups selected from the group consisting of -NH2, -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 of only carbon atoms, nitrogen atoms, and hydrogen atoms. The hydrocarbon group may be a hydrocarbon group (e.g., a chain-like saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having one to two hydrocarbon aromatic rings) that may be interrupted by oxygen atoms and / or sulfur atoms, or may be a general hydrocarbon group (e.g., a chain-like 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 modification in the present disclosure has the formula: -Y N -Z N n [In the formula, Y N is a direct bond or a group with a valence of 1+n, Z N represents a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group which may have a substituent, n is an integer between 1 and 3. and having one or more groups represented by At least one -Y N -Z N n is bonded to the nitrogen atom of the amine skeleton.

[0075] Amine modification has -Y N -Z N n The number of -Y 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 nis bonded to another group (for example, a hydrocarbon group) on the amine skeleton.

[0077] (Y N ) Y N is a direct bond or a 1+n valent group, preferably a 1+n valent group. 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, together with the amino group in the amine skeleton, one or more selected from the group consisting of an amide group, a urea group, a urethane group, and an imide group. Examples of such an amide group, a urea group, a urethane group, and an imide group include: -OC(=O)-NR'-, -NR'-C(=O)-, —NR′—C(═O)—O—, -NR'-C(=O)-NR'- -C(=O)-NR'- -C(=O)-NR'-C(=O)- [In the formula, 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)] Examples include: Y N is preferably attached 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 divalent to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a divalent to tetravalent hydrocarbon aromatic ring, and a divalent to tetravalent heterocycle. [In the formula, 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)] It may be a (1+n) valent group consisting of one or more groups selected from the group consisting of:

[0083] Y N is Y N1 and Y N2 is a (1+n) valent group consisting of one or more members selected from the group consisting of Y N1 is a group consisting of one or more selected from the group consisting of 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)), Y N2 is a group consisting of one or more members selected from the group consisting of di- to tetravalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms, di- to tetravalent hydrocarbon aromatic rings, and di- to tetravalent heterocycles, In this specification, Y N The group shown as follows has an amine skeleton on the left and Z on the right. NCombine 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 N1 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. N1 The molecular weight may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0087] Y N1 may be one or more selected from the group consisting of 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)). Y N1 Examples include: direct binding, -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′—, —C(═O)—NR′—C(═O)—, -C(=NR')-, -S-, -SO2-, -SO2NR'-, -C(OR')R'-, -C(OR')(-)2, -N(-)2 etc. [In the formula, 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).] In addition, Y 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). N2 Y may be aliphatic or aromatic. N2 may be linear, branched or cyclic.

[0090] Y N2 is a divalent or higher valent group. N2 The valence of may be, for example, 2 to 4, 2 to 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 N2is 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 hydrocarbon aromatic 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 less, 4 or less, 3 or less, or 2.

[0094] The aliphatic hydrocarbon group may have a substituent. Examples of the substituent include -OR', -N(R')2, -COOR', and a halogen atom (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 an 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 ratio of carbon atoms to the total 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 ratio of carbon atoms to the total 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', -N(R')2, -COOR', and a halogen atom (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 an 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 ratio of carbon atoms to the total 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 ratio of carbon atoms to the total 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', -N(R')2, -COOR', and a halogen atom (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 an 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 include: -Ali- -Cy- -Ali(-)2 -Cy(-)2 (-)2Ali- (-)2Cy- (-)2Ali(-)2 (-)2Cy(-)2 -Ali-Cy- -Cy-Ali- -Cy-Ali-Cy- -Ali-Cy-Ali- [In the formula, Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and Cy is a hydrocarbon aromatic ring or heterocycle.] etc.

[0100] Y N2 Specific examples include: -(CH2) p - (p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and having an unsaturated bond; a hydrocarbon group having a branched structure and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms; -(CH2) q -Cy-(CH2) r -(q and r each independently represent a number from 0 to 20, for example, 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle). etc.

[0101] Y N Examples 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 If is bivalent, -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 - and the like can be mentioned.

[0103] Y N Examples of Y N When Y 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, -Y N1 -Y N2 -Y N1 -(Y N2 -) 2、 -Y N1 -Y N2 -(Y N1 -Y N2 ​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​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 mentioned.

[0104] Y N As an example of Y N when it is tetravalent, -Y N1 (-)3, -Y N1 -Y N2 (-)3, -Y N1 -(Y N2 -)3, -Y N1 -Y <00003​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​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 -YN2 -, -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 formula, Y N1 but independently in each occurrence, direct binding, -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-, or -C(=O)-NR'- -C(=O)-NR'-C(=O)- (In the formula, 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).) 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 of *-(C=O)- —O—(C═O)—NR′— [wherein * means bonding to a nitrogen atom of an amine skeleton, R' is 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). etc.

[0108] (Z N ) Z N represents a monovalent hydrocarbon group or monovalent polysiloxane group having 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 Modification Example 1) Examples of amine-modified compounds include those of 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, in each occurrence, is independently an integer between 1 and 3, inclusive; p, in each occurrence, is independently an integer between 0 and 2, inclusive; q, independently in each occurrence, is an integer between 0 and 2, inclusive; p+q is the sum of each N(-Y N -Z N n ) p (-H) q In, 2, r is independently in each occurrence 0 or 1; s is independently in each occurrence 0 or 1; r+s is the sum of each N(-Y N -Z N n ) r (-H) s In, 1, the sum of all p's and all r's is greater than or equal to 1, t is an integer between 0 and 10. Examples of the compound include a compound represented by the following formula (amine modified example 1):

[0110] In the amine modification example 1, Y N , Z N For details of , and n, the above explanation is cited.

[0111] In the amine modification example 1, L 1 L 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 separated by oxygen atoms and / or sulfur atoms, 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. 1is preferably a cyclic group having both a ring (e.g., an aromatic ring) and a chain structure (e.g., a linear structure, ether oxygen, or thioether sulfur), and specific examples thereof 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, inclusive; q, in each occurrence, is independently an integer of 0 to 2, inclusive; and p+q is the sum of the values ​​of each N(-Y 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 may be 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 n The 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 of the 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 represents a 1+u-valent 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, in each occurrence, is independently an integer between 1 and 3, inclusive; p is an integer between 0 and 2, q is an integer between 0 and 2, p+q is 2, u is an integer between 1 and 3, The sum of p and u is greater than or equal to 1.] An example of the compound represented by the formula (amine modified compound example 2) is:

[0117] In the amine modification example 2, Y N , Z N For details of and n, the above explanation is cited.

[0118] In the amine modification example 2, L2 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, and may be a cyclic, branched, or straight-chain hydrocarbon group, 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 separated by oxygen atoms and / or sulfur atoms, 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 (e.g., an aromatic ring) and a chain structure (e.g., a linear structure, ether oxygen, or thioether sulfur), and specific examples thereof 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 or more and 2 or less, q is an integer of 0 or more and 2 or less, 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 nThe 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] (Example) Specific examples of the amine-modified compound include compounds represented by the following formula: N , Z N For details of , and n, the above explanation is cited.

[0123] [ka]

[0124] [ka]

[0125] [ka]

[0126] [ka]

[0127] [ka]

[0128] [ka]

[0129] [ka]

[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 synthetic waxes 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] [Manufacturing method] The method for producing the amine-modified product 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 the 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] [Polyol Modification] 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-repellent properties.

[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-proofing 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. The degree of polymerization refers to the number of repeating monomer units constituting the polymer.

[0135] The degree of polymerization in the present disclosure refers to an average degree of polymerization. The average degree of polymerization in the present disclosure refers to 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 the 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 (Equation 2) Hydroxyl value = 56110(n+2) / average molecular weight The hydroxyl value in the above formula (2) is a numerical value that indicates the number of hydroxyl groups contained in 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 the "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 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 formula.

[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 polysaccharide in the present disclosure is a polysaccharide obtained by modifying a polysaccharide, the degree of polymerization of the polyol-modified polysaccharide refers to the average degree of polymerization of the polysaccharide. The average degree of polymerization of a polysaccharide can be analyzed as follows. The degree of polymerization refers to the number of monosaccharide units (fructose and glucose units) in the polysaccharide. The average degree of polymerization is determined, for example, by the top of the peaks in the analysis results obtained by a conventional analytical method such as HPLC, GC, or HPAEC. The average degree of polymerization can be measured using, for example, an ULTRON PS-80N (8 × 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 × 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, 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 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 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, 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 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, 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 1 to 40 carbon atoms, which may have a substituent, or a monovalent polysiloxane group.

[0140] The residual hydroxyl group ratio 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 hydroxyl group ratio 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 ratio" refers to the proportion (mol%) of unmodified hydroxyl groups derived from the polyol.

[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. This 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] In the polyol-modified product, one or more hydroxy groups of a polyol 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 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 about 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, modified polyols are those in which one or more hydroxy groups of the polyol have the formula: -Y O -Z O n [In the formula, Y O is Y O1 and Y O2 is a (1+n) valent group consisting of one or more members selected from the group consisting of Y O1 is a group consisting of one or more selected from the group consisting of 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)), 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, Z O represents a monovalent hydrocarbon group having from 1 to 40 carbon atoms, which may have a substituent, or a monovalent polysiloxane group, n is an integer between 1 and 3. It may be substituted with a group represented by the following formula:

[0146] (Y O ) Y O is Y O1 and YO2 is a (1+n) valent group consisting of one or more members selected from the group consisting of Y O1 is a group consisting of one or more selected from the group consisting of 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)), 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 hydrocarbon aromatic 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. O 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.

[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 may include -C(=O)-NR'-, -C(=S)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SONR'-.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 The molecular weight may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0153] Y O1 may be one or more selected from the group consisting of 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)). Y O1 Examples include: direct binding, -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′—, -SO2-, -SO2NR'-, -C(OR')R'-, -C(OR')(-)2 etc. (In the formula, 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).) Examples include:

[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 may include -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO2NR'-. 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 valence of may be, for example, 2 to 4, 2 to 3, or 2.

[0158] Y O2 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. 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 hydrocarbon aromatic 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 less, 4 or less, 3 or less, or 2.

[0161] The aliphatic hydrocarbon group may have a substituent. Examples of the substituent include -OR', -N(R')2, -COOR', and a halogen atom (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 an 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 ratio of carbon atoms to the total 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 ratio of carbon atoms to the total 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', -N(R')2, -COOR', and a halogen atom (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 an 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 ratio of carbon atoms to the total 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 ratio of carbon atoms to the total 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', -N(R')2, -COOR', and a halogen atom (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 an 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 include: -Ali- -Cy- -Ali(-)2 -Cy(-)2 (-)2Ali- (-)2Cy- (-)2Ali(-)2 (-)2Cy(-)2 -Ali-Cy- -Cy-Ali- -Cy-Ali-Cy- -Ali-Cy-Ali- [In the formula, Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and Cy is a hydrocarbon aromatic ring or heterocycle.] etc.

[0167] Y O2 Specific examples include: -(CH2) p - (p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and having an unsaturated bond; a hydrocarbon group having a branched structure and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms; -(CH2) q -Cy-(CH2) r -(q and r each independently represent a number from 0 to 20, for example, 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle). etc.

[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 If is bivalent, -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 - and -Y O2 -Y O1 -Y O2 - and -Y O2 -Y O1 -Y O2 -Y O1 - etc. can be mentioned.

[0170] Y O Examples of Y O When Y 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 [[ID=A56]]-Y O1 -Y O2 (-)2, -Y O1 -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, -YO2 -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 mentioned.

[0171] ​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​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 (Example) Preferably, Y O but -OY O11 -or -OY 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, 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'-, -SO2-, -SON2NR'-, -C(OR')R'-, or -C(OR')(-)2; It may be.

[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 The molecular weight may be 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 chain, or straight chain hydrocarbon group, and may be a saturated or unsaturated (for example, saturated) aliphatic hydrocarbon group.

[0180] Y O21 Specific examples include: -(CH2) p - (p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and having an unsaturated bond; a hydrocarbon group having a branched structure and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms; -(CH2) q -Cy-(CH2) r -(q and r each independently represent a number from 0 to 20, for example, 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle). etc.

[0181] Y O12 may be —O—, —OC(═O)—, —OC(═O)—O—, —OC(═O)—NR′—, —NR′—, —NR′—C(═O)—, —NR′—C(═O)—O—, —NR′—C(═O)—NR′—, —C(═O)—O—, —C(═O)—NR′—, —SO—, —SONR′—, —C(OR′)R′—, or —C(OR′)(−)2.

[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 may be -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO2NR'-. C12 By including these groups, the liquid repellency can be improved.

[0183] (ZO ) Z O represents a monovalent hydrocarbon group or monovalent polysiloxane group having 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 The group may be substituted with a modifying group other than the following: Examples of the modifying group are anionic groups 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 a tertiary amino group, two groups bonded to the nitrogen atom are the same or different and preferably an aliphatic group having 1 to 5 carbon atoms (particularly an alkyl group), an aromatic group having 6 to 20 carbon atoms (an aryl group), or an araliphatic group having 7 to 25 carbon atoms (particularly an aralkyl group, such as a benzyl group (C6H5-CH2-)). In a quaternary amino group, three groups bonded to the nitrogen atom are the same or different and preferably an aliphatic group having 1 to 5 carbon atoms (particularly an alkyl group), an aromatic group having 6 to 20 carbon atoms (an aryl group), or an araliphatic group having 7 to 25 carbon atoms (particularly an aralkyl group, such as a benzyl group (C6H5-CH2-)). In a tertiary amino group or a 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] [Manufacturing method] The modified polyol may be prepared by reacting a modifying agent having a modifying group (or a precursor structure of the modifying group) with the hydroxy group of the 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 to 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 to the above initiators are also referred to as polyoxyalkylene polyols or oxyalkylene derivatives of polyols. Representative examples of polyether polyols include polyoxypropylene triol, obtained by addition polymerization of propylene oxide to glycerin, and polyoxypropylene polyglyceryl ether, obtained by addition polymerization of propylene oxide to 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 two or more functional carboxyl groups with a compound having two or more functional hydroxyl groups. Examples of compounds having two or more functional carboxyl groups 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 two or more functional hydroxyl groups include ethylene glycol, propylene glycol, propanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and polymers thereof.

[0210] (modifying agent) The modifying agent is preferably a compound that is reactive with polyol and has 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 as follows: Acid halide G(O=)CZ O Acid anhydride O(C(=O)-Z O )2 Carboxylic acid HO(O=)CZ O Isocyanate O=C=NZ O Thioisocyanate S=C=NZ O Epoxy (CH2OCH)CH2O-Z O Halide GZO Amine H2N-Z O Hydroxy 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 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 A-Y O -Z O n It may also be possible to use the following.

[0213] A 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 a polyol and a 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 product] 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 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 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, 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 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 apparatus and conditions. Separation column: SB-806M (8 mm x 30 mm, Shodex) Column temperature: 40℃ Mobile phase solvent: ion-exchanged water Mobile phase flow rate: 1.0 mL / min Sample concentration: 0.5 wt% Injection volume: 50μL Detector: RI detector (Waters2414, Waters)

[0217] The weight average molecular weight (Mw), number average molecular weight (Mn) and polydispersity index (Mw / Mn) of the polycarboxylic acid modified product, calculated as 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 of carboxyl groups derived from polycarboxylic acid that are modified, and may refer to the proportion (mol %) that are modified with monovalent hydrocarbon groups having 1 to 40 carbon atoms or monovalent polysiloxane groups that may have a substituent.

[0219] The residual hydroxyl group ratio of 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 hydroxyl group ratio of 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 unmodified hydroxyl groups in carboxyl groups derived from the polycarboxylic acid.

[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 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.

[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. This 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 about 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 has the following formula: -Y C -Z C n [In the formula, Y C is Y C1 and Y C2 is a (1+n) valent group consisting of one or more members selected from the group consisting of Y C1 is a group consisting of one or more selected from the group consisting of 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)), 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, Z C represents a monovalent hydrocarbon group having from 1 to 40 carbon atoms, which may have a substituent, or a monovalent polysiloxane group, n is an integer between 1 and 3. It may be substituted with a group represented by the following formula:

[0225] (Y C ) Y C is Y C1 and Y C2 is a (1+n) valent group consisting of one or more members selected from the group consisting of Y C1 is a group consisting of one or more selected from the group consisting of 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)), Y C2is 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 C 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. 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 may be -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO2NR'-. 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 The molecular weight may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0232] Y C1 may be one or more selected from the group consisting of 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)). Y C1 Examples include: direct binding, -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′—, -SO2-, -SO2NR'-, -C(OR')R'-, -C(OR')(-)2 etc. (In the formula, 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).) Examples include:

[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 may include -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO2NR'-. 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 valence of may be, for example, 2 to 4, 2 to 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 hydrocarbon aromatic 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 less, 4 or less, 3 or less, or 2.

[0240] The aliphatic hydrocarbon group may have a substituent. Examples of the substituent include -OR', -N(R')2, -COOR', and a halogen atom (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 an 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 ratio of carbon atoms to the total 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 ratio of carbon atoms to the total 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', -N(R')2, -COOR', and a halogen atom (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 an 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 ratio of carbon atoms to the total 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 ratio of carbon atoms to the total 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', -N(R')2, -COOR', and a halogen atom (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 an 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 include: -Ali- -Cy- -Ali(-)2 -Cy(-)2 (-)2Ali- (-)2Cy- (-)2Ali(-)2 (-)2Cy(-)2 -Ali-Cy- -Cy-Ali- -Cy-Ali-Cy- -Ali-Cy-Ali- [In the formula, Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and Cy is a hydrocarbon aromatic ring or heterocycle.] etc.

[0246] Y C2 Specific examples include: -(CH2) p - (p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and having an unsaturated bond; a hydrocarbon group having a branched structure and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms; -(CH2) q -Cy-(CH2) r -(q and r each independently represent a number from 0 to 20, for example, 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle). etc.

[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 If is bivalent, -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 If 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, -Y C1 -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<0​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​C2 (-)3、-Y C1 -(AND C2 -)3、-Y C1 -AND C2 -AND C1 (-)3、-Y C1 -AND C2 (-AND C1 -)3、-Y C1 -(AND C2 -AND C1 -)3、-Y C1 -AND C2 -AND C1 -AND C2 (-)3、-Y C1 -AND C2 -AND C1 -(AND C2 -) 3、 -AND C1 -AND C2 -(AND C1 -AND C2 -) 3、 -AND C1 -(AND C2 -AND C1 -AND C2 -)3; -AND C2 (-)3、-Y C2 -AND C1 (-)3、-Y C2 -(AND C1 -)3、-Y C2 -AND C1 -AND C2 (-)3、-Y C2 -AND C1 (-AND C2 -)3、-Y C2 -(AND C1 -AND C2 -)3、-Y C2 -AND C1 -AND C2 -AND C1 (-)3、-Y C2 -AND C1 -AND C2 -(AND C1 -) 3、 -AND C2 -AND C1 -(AND C2 -AND C1 -) 3、 -AND C2 -(AND C1 -AND C2 -ANDC1 -)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 (Example) Preferably, Y C but -Y C11 -or -Y C11 -Y C21 -Y C12 - wherein each symbol represents independently at each occurrence: Y C11 is -O- or -NR'-, Y C21 is a hydrocarbon group having 1 to 40 carbon atoms, 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'-, -SO2-, -SON2NR'-, -C(OR')R'-, or -C(OR')(-)2; It may be.

[0253] Y C11is 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 The molecular weight may be 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 chain, or straight chain hydrocarbon group, and may be a saturated or unsaturated (for example, saturated) aliphatic hydrocarbon group.

[0259] Y C21 Specific examples include: -(CH2) p - (p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and having an unsaturated bond; a hydrocarbon group having a branched structure and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms; -(CH2) q -Cy-(CH2) r-(q and r each independently represent a number from 0 to 20, for example, 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle). etc.

[0260] Y C12 may be —O—, —OC(═O)—, —OC(═O)—O—, —OC(═O)—NR′—, —NR′—, —NR′—C(═O)—, —NR′—C(═O)—O—, —NR′—C(═O)—NR′—, —C(═O)—O—, —C(═O)—NR′—, —SO—, —SONR′—, —C(OR′)R′—, or —C(OR′)(−)2.

[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 may be -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO2NR'-. 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 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-mentioned explanation of [Other modifying groups] in the polyol is applicable to the anionic group and / or the cationic group.

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

[0265] (Polycarboxylic acid) Polycarboxylic acids are compounds having two or more carboxyl groups and are used as raw materials for modified polycarboxylic acids. Polycarboxylic acids are compounds having two or more carboxyl groups in the molecule. Polycarboxylic acids may be aliphatic or aromatic, but are 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 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.

[0268] The carboxyl group equivalent weight 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 weight 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 weight 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, such as 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] Tetracarboxylic acids are compounds having four carboxyl groups, and examples thereof include pyromellitic acid and salts thereof.

[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] The polycarboxylic acid is represented by the following formula: CH2=C(-Q)-C(=O)-OH [In the formula, Q is a hydrogen atom, a monovalent organic group, or a halogen atom. The polymer may be a polymer containing a repeating unit derived from a compound represented by the following formula:

[0276] Q is a hydrogen atom, a monovalent organic group, or a halogen atom other than 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 preferably a compound that is reactive with polycarboxylic acid and has the above-mentioned monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group, which may have a substituent.

[0278] Examples of modifying agents are as follows: Epoxy (CH2OCH)CH2O-Z C Amine H2N-Z C Hydroxy HO-Z C [In the formula, Z C is as described above.]

[0279] Z in the structure of the above 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 A-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] 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 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 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, X a is a hydrogen atom, a monovalent organic group, or a halogen atom, Y a is a group (excluding hydrocarbon groups) consisting of at least one selected from divalent to tetravalent hydrocarbon groups having one carbon atom (particularly, -CH-, -CH=), -CH-, -O-, -C(=O)-, -S(=O)-, and -NH-; k is 1 to 3. It is preferable that the monomer is a monomer represented by the following formula:

[0289] X a X 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. 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. Y a is preferably a hydrocarbon group having one carbon atom, or a group composed of at least one selected from -CH-, -O-, -C(=O)-, -S(=O)2-, and -NH- (however, excluding hydrocarbon groups). Examples of hydrocarbon groups having one carbon atom include -CH2-, -CH= having a branched structure, and -C≡ having a branched structure.

[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'- wherein Y′ is a direct bond, —O—, —NH—, or —S(═O)—; R' is -(CH2) m - (m is an integer of 1 to 5) or -C6H4- (phenylene group). It may be.

[0292] Y a Specific examples are -O-, -NH-, -OC(=O)-, -C(=O)-NH-, -NH-C(=O)-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C6H4-, -O-(CH2) m -O-, -NH-(CH2) m -NH-, -O-(CH2) m -NH-, -NH-(CH2) m -O-, -O-(CH2) m -OC(=O)-, -O-(CH2) m -C(=O)-O-, -NH-(CH2) m -OC(=O)-, -NH-(CH2) m -C(=O)-O-, -O-(CH2) m -OC(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -C(=O)-NH-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -O-C6H4-, -O-(CH2) m -NH-S(=O)2-, -O-(CH2) m -S(=O)2-NH-, -NH-(CH2) m -OC(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2)m -C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -NH-C(=O)-NH-, -NH-(CH2) m -O-C6H4-, -NH-(CH2) m -NH-C6H4-, -NH-(CH2) m -NH-S(=O)2- or -NH-(CH2) m -S(=O)2-NH- (wherein m is 1 to 5, particularly 2 or 4).

[0293] Y a -O-, -NH-, -O-(CH2) m -OC(=O)-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -OC(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -NH-S(=O)2-, -O-(CH2) m -S(=O)2-NH-, -NH-(CH2) m -NH-S(=O)2- or -NH-(CH2) m -S(=O)2-NH- [In the formula, m is an integer of 1 to 5, particularly 2 or 4.] It is preferable that Y a is -O- or -O-(CH2) m -NH-C(=O)-, especially -O-(CH2) m It is more preferably -NH-C(=O)-.

[0294] R a is 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 monomer (a) are: Formula (a1): 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, X a1 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y a1 is —O— or —NH—.] A monomer represented by the formula: Formula (a2): 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, X a2 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y a21 is —O— or —NH—, Y a22 are each independently a direct bond or a group consisting of at least one selected from -O-, -C(=O)-, -S(=O)2-, -NH-, and -CH2-, Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms; n is 1 or 2. It is a monomer represented by the formula:

[0296] (a1) Monomer The monomer (a1) has 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, X a1is a hydrogen atom, a monovalent organic group, or a halogen atom, Y a1 is —O— or —NH—.] It is a compound represented by the formula:

[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 is -NH-. R a1 is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. a1 In the formula (I), the hydrocarbon group preferably has 12 to 30 carbon atoms, for example, 16 to 26 carbon atoms, and particularly preferably 18 to 22 carbon atoms. X 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 specific examples of the long-chain acrylate ester monomer are lauryl (meth)acrylate, stearyl (meth)acrylate, icosyl (meth)acrylate, behenyl (meth)acrylate, stearyl alpha chloroacrylate, icosyl alpha chloroacrylate, and behenyl alpha chloroacrylate. Specific preferred examples of the long-chain acrylamide monomer are stearyl (meth)acrylamide, icosyl (meth)acrylamide, and behenyl (meth)acrylamide.

[0299] (a2) Monomer Monomer (a2) is a monomer different from monomer (a1). Monomer (a2) is a (meth)acrylate or (meth)acrylamide having a group consisting of at least one selected from -O-, -C(=O)-, -S(=O)2-, -NH-, and -CH2-. The monomer (a2) has the formula: CH2=C(-X a2 )-C(=O)-Y a21 -Z(-Ya22 -R a2 ) n [In the formula, R a2 are each independently a hydrocarbon group having 6 to 40 carbon atoms, X a2 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y a21 is —O— or —NH—, Y a22 are each independently a direct bond or a group consisting of at least one selected from -O-, -C(=O)-, -S(=O)2-, -NH-, and -CH2-, Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms; n is 1 or 2. The compound may be represented by the formula: Y 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 -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-; R' is -(CH2) 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 -(CH2) l -C6H4-(CH2) l - (each l is independently an integer of 0 to 5, and -C6H4- is a phenylene group). It may be.

[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-, -O-C6H4-, -NH-C6H4-, -O-(CH2) m -O-, -NH-(CH2) m -NH-, -O-(CH2) m -NH-, -NH-(CH2) m -O-, -O-(CH2) m -OC(=O)-, -O-(CH2) m -C(=O)-O-, -NH-(CH2) m -OC(=O)-, -NH-(CH2) m -C(=O)-O-, -O-(CH2) m -OC(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -C(=O)-NH-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -O-C6H4-, -NH-(CH2) m -OC(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -C(=O)-NH-, -NH-(CH2) m-NH-C(=O)-, -NH-(CH2) m -NH-C(=O)-NH-, -NH-(CH2) m -O-C6H4-, -NH-(CH2) m -NH-C6H4- [In the formula, m is an integer of 1 to 5.] is.

[0304] Y a22 is preferably -O-, -NH-, -OC(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S(=O)2-, -S(=O)2-NH-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C6H4-. Y a22 It is more preferred that Y is -NH-C(=O)-, -C(=O)-NH-, -OC(=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 straight-chain or branched structure. Z preferably has 2 to 4 carbon atoms, and particularly 2. Specific examples of Z include a direct bond, -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH= having a branched structure, -CH2(CH-)CH2- having a branched structure, -CH2CH2CH= having a branched structure, -CH2CH2CH2CH2CH= having a branched structure, -CH2CH2(CH-)CH2- having a branched structure, and -CH2CH2CH2CH= having a branched structure. Z does not have to be a direct bond.

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

[0307] Monomer (a2) can be produced by reacting a hydroxyalkyl (meth)acrylate or a hydroxyalkyl (meth)acrylamide with a long-chain alkyl isocyanate, such as lauryl isocyanate, myristyl isocyanate, cetyl isocyanate, stearyl isocyanate, oleyl isocyanate, or 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 long-chain alkylalcohol. Examples of long-chain alkylamines include laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, and behenylamine. Examples of long-chain alkylalcohols 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 alpha chloroacrylate, behenyl alpha chloroacrylate; Stearyl (meth)acrylamide, Behenyl (meth)acrylamide;

[0309] [ka]

[0310] [ka] [ka] [ka]

[0311] [ka] [ka] [ka]

[0312] [ka] [ka] [ka] [ka]

[0313] [ka]

[0314] [ka] [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 in which the α-position is a hydrogen atom, but specific examples include a methacrylic compound in which the α-position is a methyl group and an α-chloroacrylic compound in which the α-position is a chlorine atom.

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

[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. Specifically, -C(=O)CR a211 =CH2, -CHR a211 =CH2, -CH2CHR a211 ═CH2, 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 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 It is preferred that =CH2.

[0317] R a22R 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. a22 The 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 R 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 There is only one type (e.g., R a22 is only a compound having 17 carbon atoms), or R a22 is a combination of multiple a22 and a compound having 17 carbon atoms, R a22 and a compound having 15 carbon atoms).

[0320] An example of an amide group-containing monomer is a carboxylic acid amide alkyl (meth)acrylate. Specific examples of the amide group-containing monomer include palmitic acid amidoethyl (meth)acrylate, stearic acid amidoethyl (meth)acrylate, behenic acid amidoethyl (meth)acrylate, myristate amidoethyl (meth)acrylate, laurate amidoethyl (meth)acrylate, isostearate ethyl amido(meth)acrylate, oleic acid ethyl amido(meth)acrylate, tert-butylcyclohexylcaproic acid amidoethyl (meth)acrylate, adamantanecarboxylic acid ethyl amido(meth)acrylate, naphthalenecarboxylic acid amidoethyl (meth)acrylate, anthracenecarboxylic acid amidoethyl (meth)acrylate, palmitic acid amidopropyl (meth)acrylate, stearic acid amidopropyl (meth)acrylate, palmitic acid amidoethyl vinyl ether, stearic acid amidoethyl vinyl ether, palmitic acid amidoethyl allyl ether, stearic acid amidoethyl 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% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, based on the total weight of the amide group-containing monomers. The amount of stearamidoethyl (meth)acrylate may be 90% by weight or less, 80% by weight or less, or 70% by weight 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). The monomer (b) is a monomer other than the 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, the 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) is formula: CH2=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, Y b is —O— or —NH—, R b are each independently an alkylene group having 2 to 6 carbon atoms, A b is a hydrogen atom, an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, or CH2=CX b C(=O)-present, and n is an integer from 1 to 90. It is preferable that the oxyalkylene (meth)acrylate is an oxyalkylene (meth)acrylate represented by the following formula:

[0325] Examples of monomers (b) are those of the formula: CH2=CX b C(=O)-O-(R b O) n -A bi (b1) and CH2=CX b C(=O)-O-(R b O)n -C(=O)CX b =CH2(b2), CH2=CX b C(=O)-NH-(R b O) n -A bi (b3) [In the formula, X b are each independently a hydrogen atom or a methyl group, A bi are each independently a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, R b are each independently an alkylene group having 2 to 6 carbon atoms, n is an integer between 1 and 90 ] It is preferable that the ion exchange coefficient be expressed by the following formula:

[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, of the formula -(CH) x -or-(CH2) x1 -(CH(CH3)) 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. -(CH2) x1 - and -(CH(CH3)) x2 The order of - is not limited to the depicted formula and may be random. -(R 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 2are different from each other and are alkylene groups having 2 to 6 carbon atoms, and 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 an ethylene group / propylene group combination, an ethylene group / butylene group combination, and a propylene group / butylene group combination. 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 using a polyalkylene glycol di(meth)acrylate represented by formula (b2), 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) include, but are not limited to, the following: CH2=CHCOO-CH2CH2O-H CH2=CHCOO-CH2CH2CH2O-H CH2=CHCOO-CH2CH(CH3)OH CH2=CHCOO-CH(CH3)CH2O-H CH2=CHCOO-CH2CH2CH2CH2O-H CH2=CHCOO-CH2CH2CH(CH3)OH CH2=CHCOO-CH2CH(CH3)CH2O-H CH2=CHCOO-CH(CH3)CH2CH2O-H CH2=CHCOO-CH2CH(CH2CH3)OH CH2=CHCOO-CH2C(CH3)2O-H CH2=CHCOO-CH(CH2CH3)CH2O-H CH2=CHCOO-C(CH3)2CH2O-H CH2=CHCOO-CH(CH3)CH(CH3)OH CH2=CHCOO-C(CH3)(CH2CH3)OH 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-(CH2CH(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 -(CH2CH(CH3)O)5-CH2-CH=CH2

[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-CH2CH2CH(CH3)OH CH2=CH-C(=O)-NH-CH2CH(CH3)CH2O-H CH2=CH-C(=O)-NH-CH(CH3)CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH(CH2CH3)OH 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-CH2CH2CH(CH3)OH CH2=C(CH3)-C(=O)-NH-CH2CH(CH3)CH2O-H CH2=C(CH3)-C(=O)-NH-CH(CH3)CH2CH2O-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) is X 2 is a hydrogen atom. Monomer (b) is particularly preferably hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or hydroxyethyl acrylamide.

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

[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 include an amino group, preferably a tertiary amino group or a quaternary amino group. In the tertiary amino group, the two groups bonded to the nitrogen atom are preferably the same or different and are an aliphatic group (particularly an alkyl group) having 1 to 5 carbon atoms, an aromatic group (an aryl group) having 6 to 20 carbon atoms, or an araliphatic group (particularly an aralkyl group, such as a benzyl group (CH-CH-)) having 7 to 25 carbon atoms. In the quaternary amino group, the three groups bonded to the nitrogen atom are preferably the same or different and are an aliphatic group (particularly an alkyl group) having 1 to 5 carbon atoms, an aromatic group (an aryl group) having 6 to 20 carbon atoms, or an araliphatic group (particularly an aralkyl group, such as a benzyl group (CH-CH-)) having 7 to 25 carbon atoms. 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, 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 salts) 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 monomers The vinyl polymer may have a repeating unit derived from a halogenated olefin monomer (d). The halogenated olefin monomer (d) may not have a fluorine atom. The halogenated olefin monomer (d) is preferably an olefin having 2 to 20 carbon atoms and substituted with 1 to 10 chlorine, bromine, 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 1 to 5 chlorine atoms. Preferred examples of the halogenated olefin monomer (d) include vinyl halides such as vinyl chloride, vinyl bromide, and 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 water repellency durability). The presence of repeating units derived from the halogenated olefin monomer (d) enhances the washing durability of the vinyl polymer.

[0345] (e) Crosslinkable monomer The vinyl polymer has a crosslinkable monomer having at least two reactive groups and / or ethylenically unsaturated double bonds (preferably, (meth)acrylate groups), and the crosslinkable monomer (e) may be a monomer not containing a fluorine atom or a compound not containing a fluorine atom. The crosslinkable monomer (e) may be a compound having at least two ethylenically unsaturated double bonds (preferably, (meth)acrylate groups), or a compound having 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, and a carboxyl group.

[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, for example, have 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 cyclic hydrocarbon groups include cyclohexyl, t-butylcyclohexyl, adamantyl, 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl, bornyl, isobornyl, norbornyl, dicyclopentanyl, dicyclopentenyl, benzyl, phenyl, naphthyl, 2-t-butylphenyl, residues obtained by removing one or more hydrogen atoms from these groups (e.g., cyclohexylene, adamantylene, phenylene, naphthylene, etc.), and groups that 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, but 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 the monomers (a) to (g) constituting the repeating units of the vinyl polymer is not particularly limited, but examples are as follows (brackets are 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, other monomers (g) may be used in combination with the above combination. In the case of pulp products, it is preferable to use the monomers (a), (b) and (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 repeat 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 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 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 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 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 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 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 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 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 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 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, such as 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 3000 parts by weight, for example, 50 to 2000 parts by weight, relative to 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 50-80°C for 1-20 hours with stirring. Polymerization initiators 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 of 0.01-10 parts by weight per 100 parts by weight of 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 an amount ranging from 0.5 to 20 parts by weight per 100 parts by weight of the 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 emulsifiability and copolymerizability.

[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〕 An example of a liquid-repellent compound will be described below, which is an oil. 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., 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 its 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, 100000 or more, 300000 or more, or 500000 or more; or 10000000 or less, 75000000 or less, 50000000 or less, 3000000 or less, 1000000 or less, 750000 or less, 5000000 or less, 300000 or less, 100000 or less, 750000 or less, 5 ... or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 100000 or less, 75000 or less,

[0374] [Synthetic oil] Synthetic oils are oils (oily compounds) 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] Vegetable and animal oils may be liquid or solid (wax) at room temperature. These include 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, beef tallow, lard (pork fat), mutton tallow, beef foot oil, whale oil, salmon oil, bonito oil, herring oil, cod oil, and hydrogenated oils thereof; rice wax, carnauba wax, sunflower wax, candelilla wax, and 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 include 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 trideca-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 trideca-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] An example of an alkanolamide is formed from a fatty acid and an alkanolamine. The alkanolamide may be a monoalkanolamide or a dialkanolamine. 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. The alkanolamine may be an alkanol 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 (having, for example, 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 structure of the alkylene oxide adduct moiety and the polyalkylene glycol moiety is polyoxyethylene (POE), polyoxypropylene (POP), or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred. Additionally, the nonionic dispersant may be free of aromatic groups.

[0392] The nonionic dispersant has the formula: R 1 O-(CH2CH2O) 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, R 2 are independently the same or different and are alkylene groups having 3 or more carbon atoms (e.g., 3 to 10), R 3 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms, p is a number greater than or equal to 2, q is a number of 0 or 1 or more. The compound may be a compound represented by the formula:

[0393] R 1R preferably has 8 to 20 carbon atoms, particularly 10 to 18 carbon atoms. 1 Preferred specific examples include an octyl group, a nonyl group, a trimethylnonyl group, a lauryl group, a tridecyl group, an oleyl group, and a stearyl group. R 2 Examples of the alkyl group include 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 (C7-C 19 ) or alkyl (C 12 -C 18 ) 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 the polyoxyethylene block can be 5 to 80% by weight, for example 30 to 75% by weight, 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 include 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, amino alcohol 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 polymeric cationic dispersants such as polyquaternium-1 to -47. Examples of cationic dispersants include alkylamine salts and quaternary ammonium salts.

[0399] Low molecular weight cationic dispersants are 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, X is an anionic group. R 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 (alkyl having 4 to 40 carbon atoms).

[0400] Specifically, the low molecular weight cationic dispersant is represented by the formula: R 1 p -N + R 2 q X - [In the formula, R 1 is C12 or higher (e.g., C 12 ~C 50 ) is a linear and / or branched aliphatic (saturated and / or unsaturated) group of R 2 is H or a C1-4 alkyl group, a benzyl group, or a polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (particularly 2, especially 3) to 50) (CH3 and C2H5 are particularly preferred), X is a halogen atom (e.g., chlorine), or a C1-C4 fatty acid salt, or a C1-C4 sulfonate; p is 1 or 2, q is 2 or 3, and p+q=4. R 1 may have 12 to 50 carbon atoms, for example, 12 to 30 carbon atoms.

[0401] 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 cationic groups (e.g., ammonium groups, quaternary ammonium groups). Examples of polymeric cationic dispersants 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 include an anionic dispersant. The anionic dispersant may be an anionic surfactant. The dispersant may be free of 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 dispersants, phosphate mono- or diester dispersants, and sulfosuccinates. An example of an anionic dispersant is a carboxylate (e.g., a fatty acid salt).

[0406] [Amphoteric dispersant] The dispersant may comprise 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 include 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 using 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] [Excipients] 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 excipients] The excipient may include 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, sugar alcohols, etc. Decomposition products by enzymes and the like are also included in the derivatives. 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 nanofibers may be unmodified cellulose nanofibers or anionized or cationized nanofibers. For example, the cellulose nanofibers may be carboxymethyl cellulose nanofibers.

[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, magnesium carbonate, and the like.

[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 the 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 the 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 the 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 the 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 the 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 the 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 the 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 break down the oil-proofing composition into finer particles 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 include 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 include 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, polyol such as glycol-based solvent, ether form of polyol (e.g., monoether form), etc.). These may be used alone or in combination of two or more.

[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] [Silicone amount] 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 of the present disclosure may contain a wax, which can impart good liquid repellency to a 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-eicosene, 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 include a curing agent (an active hydrogen-reactive compound or an 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. A 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). A 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 are 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.The use of a blocked polyisocyanate compound is preferable for reasons such as its relative stability in solution and its usability 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.

[0452] The epoxy compound is a compound having an epoxy group. Examples of the epoxy compound include epoxy compounds having a polyoxyalkylene group, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether. The chloromethyl group-containing compound is a compound having a chloromethyl group. Examples of the chloromethyl group-containing compound include chloromethyl polystyrene. The carboxyl group-containing compound is a compound having a carboxyl group. Examples of the carboxyl group-containing compound include (poly)acrylic acid and (poly)methacrylic acid.

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

[0454] [Amount of hardener] 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 ingredients] The oil-proofing agent composition may contain other components in addition to the above components. Examples of the other components include polysaccharides, paper strength agents, flocculants, retention aids, coagulants, binder resins, sizing agents, fillers, preservatives, antibacterial agents, deodorizers, fragrances, etc. These may be used alone or in combination of two or more. In addition to the above-mentioned components, other components that can be blended include other water and / or oil repellents, dispersants, softeners, flame retardants, paint fixing agents, drying speed regulators, crosslinking agents, film-forming aids, compatibilizers, viscosity modifiers, pH adjusters, insect repellents, antifoaming agents, shape-retaining agents, clay, pigments, polymer dispersants, stain release agents, enzymes such as cellulase, amylase, protease, lipase, and keratinase as fiber surface modifiers, foam inhibitors, etc. These may be used alone or in combination of two or more.

[0456] [Polysaccharide] 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, 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-formaldehyde condensates, dimethyldiallylammonium chloride polymers, and olefin / maleic anhydride polymers.

[0458] [Sizing agent] 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 acrylates.

[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 their 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 ion-conductive groups may also be used. These may be used alone or in combination.

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

[0461] [UV 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] Antibacterial agents are components that have the effect of suppressing the growth of bacteria on fibers and further suppressing the generation of unpleasant odors caused by microbial decomposition products. Examples of antibacterial agents include cationic disinfectants such as quaternary ammonium salts, bis-(2-pyridylthio-1-oxide) zinc, polyhexamethylene biguanidine hydrochloride, 8-oxyquinoline, and polylysine.

[0463] [Deodorant] Examples of deodorizing agents 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 methylglycinediacetate described in WO 2012 / 090580).

[0464] [Amount of other ingredients] 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 substrate. The pulp composition of the present disclosure may have excellent oil 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 fir and pine, and hardwood kraft pulp obtained from species such as acacia, eucalyptus, beech, and poplar (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 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), and thermomechanical pulp (TMP).Furthermore, waste paper pulp includes disintegrated waste paper pulp, disintegrated and deinked waste paper pulp, and disintegrated, deinked, and bleached waste paper pulp, which are produced from brown paper, recycled kraft envelope paper, magazine paper, newspaper paper, flyer paper, office paper, corrugated cardboard, white paper, Kent paper, imitation paper, and land certificate paper.

[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, kozo, and the like. [Synthetic fiber] The pulp composition may contain synthetic fibers, such as polyester fibers typified by polyamide fibers and polyethylene terephthalate fibers (hereinafter also referred to as PET or PET fibers), acrylic fibers, polyolefin fibers such as polyethylene fibers and polypropylene fibers, aramid fibers, polyethylene naphthalate fibers, polybutylene terephthalate fibers, polyphenylene sulfide fibers (hereinafter also referred to as PPS fibers), polyacetal fibers, liquid crystal polymer fibers, glass fibers, and polyimide fibers. Examples of pulp include those obtained from the above.

[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, It is preferably 10 μm or more, more preferably 15 μm or more, and also preferably 5 μm or more. 0 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] [Pulp base material form] The form of the pulp base material when the liquid-repellent compound is added may be pulp alone, pulp slurry, pulp products, etc., and 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% 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, or 90% 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 pulp base material in the pulp composition is 30% by weight 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% by weight 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 comprise a liquid medium, which may be water, an organic solvent, or a mixture of water and an organic solvent, typically an aqueous medium, particularly water, or may comprise a liquid medium derived from an oil-proofing 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 the section "Oil-proofing composition" is incorporated herein by reference.

[0483] [Amount of liquid repellent compound] The amount of the liquid repellent compound 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, preferably 0.5% by weight or more, and may be 25% by weight or less, 20% by weight or less, 15% by weight or less, 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, for example, 15% by weight or less, 5.0% by weight or less, or 3.0% by weight 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, 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 (for example, 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 2 More than 0.03g / m 2 More than 0.05g / m 2 More than 0.1g / m 2 More than 0.3g / m 2 More than 0.5g / m 2 or more, or 1.0 g / m 2 or more, and 5.0 g / m 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 dispersants in the section "Oil-proofing composition" is incorporated herein by reference.

[0489] [Amount of dispersant] The amount of dispersant 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, based on the pulp base material.

[0490] [Paper strength agent] The pulp composition may include a strength agent. Examples of strength agents 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 hydroxyl groups or cationic groups have 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 resin, melamine resin, urea-formaldehyde resin, and melamine-formaldehyde resin; 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-modified polyvinyl alcohol, cation-modified polyvinyl alcohol, diacetone-modified polyvinyl alcohol, and terminal alkyl-modified polyvinyl alcohol; Examples include styrene-butadiene copolymer, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, polyacrylic ester, fatty acid diamide, polyethyleneimine resin, and ketone aldehyde resin. 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 and 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] The binder may contain a water-soluble polymer such as casein, or a binder such as 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.

[0495] [Pigment] 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, as well as 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; and various solid, hollow, or through-hole particles.

[0496] [Other additives] In addition to the above, the pulp composition may contain other additives such as paper-related chemicals 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 the 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, molded pulp products, 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 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 of manufacturing oil-resistant composition> The method for producing the oil-proofing 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 The precursor mixture is subjected to a heat treatment or a drying treatment to obtain a solid oil-proofing composition.

[0500] [Mixing process] 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 can be performed using a medicine spoon. Also, known granulation devices capable of mixing and / or kneading can 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 and drying processes] The heating and drying steps 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 can be obtained in solid form.

[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 process] 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 is 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 manufacturing treated textile or paper products> The method for producing an article treated with the oil-proofing composition of the present disclosure includes 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 the 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] [Base material] 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 of 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 of 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, and plaster.

[0517] When the substrate is glass, the 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 or a multi-layer. Examples of inorganic substances that can be used for the anti-reflection layer include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, CeO2, MgO, Y2O3, SnO2, MgF2, and WO3. These inorganic substances may be used alone or in combination (e.g., as a mixture) of two or more of these. When a multi-layer anti-reflection layer is used, it is preferable to use SiO2 and / or SiO for the outermost layer. When the article to be manufactured is an optical glass component for a touch panel, a transparent electrode, such as a thin film using indium tin oxide (ITO) or indium zinc oxide, may be formed on a portion of the surface of the substrate (glass). In addition, the substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomizing film layer, a hard coating film layer, a polarizing film, a phase difference film, and a liquid crystal display module, etc., depending on its specific specifications.

[0518] [Processing method] The oil-proofing 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-proofing 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 with the solid components of the oil-proofing composition adhered thereto. If necessary, the composition may be applied together with an appropriate crosslinking agent and cured. The oil-proofing 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 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 changed 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 known method for treating a substrate with a liquid. The substrate may be immersed in the oil-proofing composition, or the 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 at low temperatures (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 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] [Processing of paper products] Examples of paper substrates include paper, paper containers, and paper molded articles (such as pulp molds).

[0521] A method for producing a paper product according to the present disclosure includes mixing the oil-proofing composition according to the present disclosure with a liquid medium to prepare an aqueous dispersion of the oil-proofing composition; This involves treating the paper with an aqueous dispersion by external or internal 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. As the liquid medium, the liquid medium of the present disclosure can be used, and for example, water may be used.

[0523] The amount of the oil-proofing composition in the dispersion of the oil-proofing composition of the present disclosure is 1% by weight or more, and 3% by weight or more. The amount of the oil anti-oil composition in a dispersion of the oil anti-oil composition of the present disclosure may be 50% by weight or less, 40% by weight or less, 30% by weight or less, 25% by weight or less, 20% by weight or less, or 15% by weight or less.

[0524] The amount of the liquid repellent compound in the dispersion of the oil-proofing composition of the present disclosure is 1% by weight or more, and 3% by weight or more. The amount of the liquid repellent compound in the dispersion of the oil proof agent composition of the present disclosure may be 50% by weight or less, 40% by weight or less, 30% by weight or less, 25% by weight or less, 20% by weight or less, or 15% by weight 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] The size press for external addition treatment can be divided into the following types depending 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. The paper is then passed through this pool to apply the size liquid to both sides of the paper. Other application methods include the gate roll type, in which the size liquid is applied using a surface transfer method, and the rod metering size press. In the pond-type two-roll size press, the size liquid easily penetrates into the paper, while in the surface transfer type, the size liquid components tend to remain on the paper surface. In the surface transfer type, the coating layer tends to remain on the paper surface compared to the pond-type two-roll size press, and a larger coating layer is formed on the surface than in the pond-type two-roll size press. In the present disclosure, performance can be imparted to paper even when the former pond-type two-roll size press is used. Paper treated in this manner can exhibit excellent oil resistance, water resistance, etc. by simply drying at room temperature or a high temperature, optionally followed by heat treatment, which can be performed at temperatures up to 300°C, for example up to 200°C, particularly in the range of 80°C to 180°C, depending on the paper properties.

[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 within 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 corrugating media, 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 include bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, groundwood pulp, mechanical pulp, or thermomechanical pulp. Any of bleached or unbleached high-yield pulp, recycled paper pulp from newspapers, magazines, corrugated cardboard, deinked paper, etc. can be used. Also, mixtures of the above pulp raw materials with synthetic fibers such as asbestos, polyamide, polyimide, polyester, polyolefin, polyvinyl alcohol, etc. can 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 (e.g., starch, modified starch, carboxymethyl cellulose, 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 preferred. If necessary, the oil-proofing agent composition may 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 , especially 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 It is preferable that: 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 external addition, oil resistance can also be imparted to paper using a so-called pond-type two-roll size press process, in which a treatment solution is stored 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, paper 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, paper strength agents, flocculants, retention agents, or coagulants (solids or active ingredients) can generally be used in an amount of 0.1 to 10 wt. % (e.g., 0.2 to 5.0 wt. %) based on the pulp. In the case of a paper substrate containing a cationic additive (e.g., a sizing agent, paper strength agents, flocculants, retention agents, or coagulants), the oil-proofing 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 (e.g., 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 durability 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 textile products is not limited, and textile products can be pretreated by conventionally known methods. 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 known methods 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 textile products, a method for pretreating textile products with the above-mentioned treatment agent will be described in detail below.

[0539] The pretreatment method for textile products is to add -SO3M to the fibers. 1 (In the formula, M 1 represents a monovalent cation), -COOM 2 (In the formula, M 2 represents a monovalent cation), and -OP(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. 2Examples of X include H, K, Na, and an ammonium ion 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] The fibers containing the specific functional groups (hereinafter, sometimes referred to as "functional group-containing fibers") can be prepared, for example, by the following method. (i) A compound having the specific functional group is attached to a fiber material. The attachment of the compound may be in a state where a part of the compound is chemically bonded to a part of the fiber, to the extent that a sufficient amount of the specific functional group remains. (ii) A fiber is prepared in which the specific functional group is 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 of fibers (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 textile materials 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 -SO3M 1A 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] [ka] [where, X 2 Ha-SO3M 3 (In the formula, M 3 represents a monovalent cation) or a group represented by the following general formula, and n is an integer of 20 to 3000.

[0547] [ka] [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 reacting 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 in 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.

[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] Above -OP(O)(OX 1 )(OX 2 ) includes, for example, phosphate ester compounds represented by the following general formula: [ka] [where, X 1 or X 2 is the same as 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 solution include, for example, padding, immersion, spraying, and coating. Examples of padding include methods using padding devices, such as those 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, such as those 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, such as those 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 treatments include air spraying, which sprays the treatment liquid in a mist form using compressed air, and methods using hydraulic atomization air spraying. The treatment conditions, such as the concentration of the treatment liquid and the heat treatment after application, can be appropriately adjusted taking into account various conditions, such as the purpose and performance. Furthermore, if the pretreatment liquid contains water, it is preferable to dry the pretreatment liquid after application to the fiber material to remove the water. The drying method is not particularly limited, and can be either a dry heat method or a wet heat method. The drying temperature is also not particularly limited, and can be,...

Claims

1. An oil-resistant composition comprising a liquid-repellent compound, a dispersant, and an excipient, the composition being solid.

2. 2. The oil-resistant 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. 2. The oil-proofing composition according to claim 1, 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.

4. the liquid repellent compound is selected from the group consisting of an amine-modified compound, a polyol-modified compound, and a polycarboxylic acid-modified compound; The amine-modified compound is an amine backbone, and The following formula: -Y Ｎ -Z Ｎ ｎ [Y Ｎ Is Y Ｎ１ and Y Ｎ２ is a (1+n) valent group consisting of one or more groups selected from the group consisting of Y 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), 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, Z Ｎ represents a monovalent hydrocarbon group having from 1 to 40 carbon atoms or a monovalent polysiloxane group which may have a substituent, n is an integer of 1 or more and 3 or less. and having one or more groups represented by At least one -Y Ｎ -Z Ｎ ｎ is bonded to a nitrogen atom of the amine skeleton; The polyol modification may be achieved by modifying one or more hydroxy groups of the polyol to the following formula: -Y Ｏ -Z Ｏ ｎ [In the formula, Y Ｏ Is Y Ｏ１ and Y Ｏ２ is a (1+n) valent group consisting of one or more groups selected from the group consisting of Y 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), 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, Z Ｏ represents a monovalent hydrocarbon group having from 1 to 40 carbon atoms or a monovalent polysiloxane group which may have a substituent, n is an integer of 1 or more and 3 or less. is a compound substituted with a group represented by The polycarboxylic acid modified product is a polycarboxylic acid modified product in which a hydroxy group of one or more carboxyl groups of the polycarboxylic acid is substituted by the following formula: -Y Ｃ -Z Ｃ ｎ [In the formula, Y Ｃ Is Y Ｃ１ and Y Ｃ２ is a (1+n) valent group consisting of one or more groups selected from the group consisting of Y 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), 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, Z Ｃ represents a monovalent hydrocarbon group having from 1 to 40 carbon atoms or a monovalent polysiloxane group which may have a substituent, n is an integer of 1 or more and 3 or less. A compound substituted with a group represented by the formula: The oil-resistant composition according to claim 1.

5. The amine skeleton is Ethylenediamine, propylenediamine, butylenediamine, pentanediamine, hexamethylenediamine; Diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine; 2-amino-1,3-propanediol; o-, m- or p-xylylenediamine; 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 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, and 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, isomaltodextrin, gellan gum, tamarind seed gum; Kojic acid, quinic acid, chlorogenic acid, gluconic acid; Glucosamine; Ascorbic acid, inositol; Catechin, quercetin, anthocyanins; Glycerin, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, trimethylolpropane, trimethylolethane; 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; The polycarboxylic acid Citric acid, malic acid, glutaric acid, adipic acid, phthalic acid, alginic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, aldaric acid; Tricarballylic acid, t-aconitic acid, trimellitic acid; Pyromellitic acid; The following formula CH ２ =C(-Q)-C(=O)-OH [In the formula, Q is a hydrogen atom, a monovalent organic group, or a halogen atom. a polymer containing a repeating unit derived from a compound represented by the formula: The oil-proofing composition according to claim 4, wherein the compound is at least one selected from the group consisting of methyl methyl acrylate and derivatives thereof.

6. 4. The oil-proofing composition according to claim 3, wherein the other solid oil comprises 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.

7. 2. The oil-proofing composition according to claim 1, 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, relative to 100 parts by weight of the liquid-repellent compound.

8. 2. The oil-proofing composition according to claim 1, 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.

9. The excipient may be glucose, fructose, galactose, dextrin, sucrose, lactose, hydroxyethyl cellulose, hydroxypropyl cellulose, 2. The oil-proofing composition according to claim 1, comprising at least one selected from the group consisting of 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, Agrobacterium sinoglycan, cationized guar gum, polyvinyl alcohol, polyacrylic acid, and sodium polyacrylate.

10. 2. The oil-proofing composition according to claim 1, 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.

11. 2. The oil-proofing composition according to claim 1, wherein the oil-proofing composition is in the form of a tablet, and the particle size thereof is 2,000 to 100,000 μm.

12. 2. The oil-proofing composition according to claim 1, wherein the water content of the oil-proofing composition is 0.01% by weight to 20% by weight.

13. 2. The oil-proofing composition according to claim 1, 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 compound, The amine-modified compound 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 independently in each occurrence an alkyl group having from 14 to 24 carbon atoms; L 1 is independently in each occurrence a divalent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms; p, in each occurrence, is independently an integer between 1 and 2, inclusive; q is independently in each occurrence 0 or 1; p+q is each N(-C(=O)-Z N ) p (-H) q In r is independently in each occurrence 0 or 1; s is independently in each occurrence 0 or 1; r+s is each N(-C(=O)-Z N ) r (-H) s In t is an integer of 0 to 3. The oil-proofing composition according to claim 1, wherein the compound is represented by the formula:

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

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

17. mixing a liquid repellent compound, a dispersant, an excipient, and a liquid medium to obtain a precursor mixture; and and subjecting the precursor mixture to a heat treatment or a drying treatment to obtain a solid oil-proofing composition.

18. 18. A method for producing the oil-proofing composition of claim 17, comprising compressing the oil-proofing composition into tablets.

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

20. Mixing the oil-proofing composition according to any one of claims 1 to 14 with water to prepare an aqueous dispersion of the oil-proofing composition; A method for producing a pulp mold, comprising filling a mold with the aqueous dispersion and a pulp base material, and allowing water to permeate out of the mold to form the pulp.

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