Oil resistant agent composition

Abstract

To provide a solid oil resistant agent composition that enables provision of an oil resistant agent aqueous dispersion upon use.SOLUTION: Provided is a solid oil resistant agent composition that contains a liquid-repellent compound, a dispersant, and a filler.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to an oil-resistant agent composition.

Background Art

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

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] The powdery papermaking composition of Patent Document 1 is provided as an aqueous dispersion, stored, and considered to be used at an appropriate time and place. The aqueous dispersion of the powdery papermaking composition may cause the powdery papermaking composition to settle during storage or use after being provided. The aqueous dispersion in which sedimentation has occurred may not achieve the desired performance during use.

Means for Solving the Problems

[0005] The present disclosure provides an oil-resistant agent composition which is solid and can provide an oil-resistant agent aqueous dispersion during use.

[0006] The present disclosure includes the following aspects: [Item 1] An oil-resistant agent composition which is solid and contains a liquid-repellent compound, a dispersant, and an excipient. [Item 2] The oil-resistant agent composition according to Item 1, wherein the liquid-repellent compound has a hydrocarbon group or a polysiloxane group having 6 to 40 carbon atoms. [Item 3] The oil-resistant agent composition according to claim 1 or 2, wherein the liquid-repellent compound contains at least one selected from the group consisting of an amine-modified product, a polyol-modified product, a polycarboxylic acid-modified product, and other solid oils. [Claim 4] The liquid-repellent compound is selected from the group consisting of an amine-modified product, a polyol-modified product, and a polycarboxylic acid-modified product, The amine-modified product is an amine skeleton, and the following formula: -Y N -Z N n [Y N is a 1 + n-valent group composed of one or more selected from the group consisting of Y N1 and Y N2 ; Y N1 is a group composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -C(=S)-, -S-, -S(=O)2-, -NR'-, -C(OR')R'-, -C(OR')(-)2, and -N(-)2 (wherein R' is, in each occurrence, independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms); Y N2 is a group composed of one or more selected from the group consisting of an optionally substituted aliphatic hydrocarbon group having 2 to 4 carbon atoms, an optionally substituted hydrocarbon aromatic ring, and an optionally substituted heterocyclic ring having 2 to 4 carbon atoms; Z N is an optionally substituted monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group; n is an integer of 1 or more and 3 or less.] and has one or more groups represented by at least one -Y N -Z N n is bonded to the nitrogen atom of the amine skeleton; The polyol-modified product has one or more hydroxy groups of the polyol represented by the following formula: -Y O -ZO n [wherein, Y O is a 1 + n-valent group composed of one or more selected from the group consisting of Y O1 and Y O2 and is a group composed of one or more selected from the group consisting of Y Y O1 is a group composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -C(=S)-, -S-, -S(=O)2-, -NR'-, -C(OR')R'-, -C(OR')(-)2, and -N(-)2 (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 composed of one or more selected from the group consisting of an optionally substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms and 2 to 4 valences, an optionally substituted hydrocarbon aromatic ring, and an optionally substituted heterocyclic ring having 2 to 4 valences. Z O is an optionally substituted monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group. n is an integer of 1 or more and 3 or less.] is a compound substituted with a group represented by; the polycarboxylic acid modifier is obtained by replacing the hydroxy group of one or more carboxyl groups of the polycarboxylic acid with the following formula: -Y C -Z C n [wherein, Y C is a 1 + n-valent group composed of one or more selected from the group consisting of Y C1 and Y C2 and is a group composed of one or more selected from the group consisting of Y Y C1 is a group composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -C(=S)-, -S-, -S(=O)2-, -NR'-, -C(OR')R'-, -C(OR')(-)2, and -N(-)2 (wherein, R' is independently, in each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms). Y C2 is a group composed of one or more selected from the group consisting of a divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a divalent hydrocarbon aromatic ring which may have a substituent, and a divalent heterocyclic ring which may have a substituent, Z C is a monovalent hydrocarbon group having 1 or more and 40 or less carbon atoms which may have a substituent or a monovalent polysiloxane group, n is an integer of 1 or more and 3 or less.] is a compound substituted with a group represented by; The oil-resistant agent composition according to any one of Items 1 to 3. [Item 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, 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, isomaltooligosaccharide, gellan gum, tamarind seed gum; Cochinic acid, cinnamic acid, chlorogenic acid, gluconic acid; Glucosamine; Ascorbic acid, inositol; Catechin, quercetin, anthocyanin; Glycerin, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, trimethylolpropane, trimethylolethane; 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, wherein the polycarboxylic acid is Citric acid, malic acid, glutaric acid, adipic acid, phthalic acid, alginic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, aldic acid; Tricarballylic acid, t-aconitic acid, trimellitic acid; Pyromellitic acid; The following formula CH2=C(-Q)-C(=O)-OH [wherein Q is a hydrogen atom, a monovalent organic group, or a halogen atom excluding a fluorine atom.] A polymer containing a repeating unit derived from the compound represented by And at least one selected from the group consisting of derivatives thereof, the oil-resistant agent composition according to item 4. [Item 6] The oil-resistant agent composition according to item 3, wherein the other solid oil contains at least one selected from rice wax, carnauba wax, hydrogenated castor oil, hydrogenated soybean oil, hydrogenated jojoba oil, hydrogenated rapeseed oil, sunflower wax, candelilla wax, 12-hydroxystearic acid, and ivy wax. [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 with respect to 100 parts by weight of the liquid-repellent compound. [Item 8] The oil-resistant agent composition according to any one of items 1 to 7, wherein the excipient contains at least one selected from the group consisting of saccharides, polysaccharides and polysaccharide derivatives, water-soluble vinyl polymers and their salts, and silicates. [Item 9] The excipient is glucose (dextrose), fructose, galactose, dextrin, sucrose, lactose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, carboxymethyl cellulose, starch, modified starch, pullulan, guar gum, locust bean gum, tamarind seed gum, chitosan, gum arabic, karaya gum, pectin, konjac mannan, carrageenan, isomalto dextrin, mannitol, sorbitol, agar, alginic acid, chitosan gum, gellan gum, Agrobacterium sinoglycan, cationized guar gum, polyvinyl alcohol, polyacrylic acid, and sodium polyacrylate. The oil-resistant agent composition according to any one of items 1 to 8, containing at least one selected from the group consisting of. [Item 10] The oil-resistant agent composition according to any one of items 1 to 9, wherein the dispersant contains at least one selected from the group consisting of nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants, and polymer dispersants. [Item 11] The oil-resistant agent composition according to any one of items 1 to 10, wherein the oil-resistant agent composition is in tablet form and its particle size is 2000 to 100000 μm. [Item 12] The oil-resistant agent composition according to any one of items 1 to 11, wherein the water content of the oil-resistant agent composition is 0.01% by weight to 20% by weight. [Item 13] The oil-resistant 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. [Item 14] The liquid-repellent compound is an amine-modified product, The amine-modified product has the following formula: N(-C(=O)-Z N ) p (-H) q -L 1 -[N(-C(=O)-Z N ) r (-H) s -L 1 -] t -N(-C(=O)-Z N ) p (-H) q [In the formula, Z N is, in each occurrence, independently an alkyl group having 14 to 24 carbon atoms, L 1 is, in each occurrence, independently a divalent aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms, p is, in each occurrence, independently an integer of 1 or more and 2 or less, q is, in each occurrence, independently 0 or 1, p + q is 2 in each N(-C(=O)-Z N ) p (-H) q , r is, in each occurrence, independently 0 or 1, s is, in each occurrence, independently 0 or 1, r + s is 1 in each N(-C(=O)-Z N ) r (-H) s , t is an integer of 0 or more and 3 or less.] The oil-resistant agent composition according to any one of items 1 to 13, which is a compound represented by . [Item 15] An oil-resistant paper containing a liquid-repellent compound, a dispersant, and an excipient in the oil-resistant agent composition according to any one of Items 1 to 14. [Item 16] The oil-resistant paper according to Item 15, which is a pulp-molded product. [Item 17] Mixing a liquid-repellent compound, a dispersant, an excipient, and a liquid medium to obtain a precursor mixture, and A method for producing an oil-resistant agent composition, comprising subjecting the precursor mixture to a heat treatment or a drying treatment to obtain a solid oil-resistant agent composition. [Item 18] The method for producing an oil-resistant agent composition according to Item 17, comprising tableting the oil-resistant agent composition. [Item 19] Mixing the oil-resistant agent composition according to any one of Items 1 to 14 with water to prepare an aqueous dispersion of the oil-resistant agent composition, A method for producing a paper product, comprising treating paper by external addition treatment or internal addition treatment using the aqueous dispersion. [Item 20] Mixing the oil-resistant agent composition according to any one of Items 1 to 14 with water to prepare an aqueous dispersion of the oil-resistant agent composition, A method for producing a pulp mold, comprising filling the aqueous dispersion and a pulp base material into a mold and permeating water outside the mold to form the pulp. [Advantages of the Invention]

[0007] The oil-resistant agent composition of the present disclosure is solid and can provide an oil-resistant agent aqueous dispersion during use. The oil-resistant agent composition of the present disclosure can be provided in a solid state and does not require storage as an aqueous dispersion until use. [Modes for Carrying Out the Invention]

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

[0009] As used herein, the term "hydrocarbon group" means a group containing carbon and hydrogen, and is a group obtained by removing a hydrogen atom from a hydrocarbon. Such a hydrocarbon group is not particularly limited, but is C 1-20 Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The above "aliphatic hydrocarbon group" may be linear, branched or cyclic, and may be saturated or unsaturated. Further, 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, whether or not expressions such as "independently at each occurrence", "independently of each other", "independently of one another" or similar expressions are explicitly described, unless otherwise stated as an exception, when a term (symbol) that may appear multiple times in a chemical structure is defined, the definition is applied independently for each occurrence.

[0011] The chemical structures described in this specification should be understood not to include chemical structures that are recognized by those skilled in the art as chemically impossible or extremely unstable.

[0012] <Oil-resistant agent composition> The oil-resistant composition of the present disclosure contains a liquid-repellent compound, a dispersant, and an excipient, and is solid. The oil-resistant composition in the present disclosure adheres to a substrate (especially a pulp substrate) and can impart liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or antifouling properties to the substrate, and can also function as a water-resistant agent, an oil-resistant agent, a water-repellent agent, an oil-repellent agent, and / or an antifouling agent. The oil-resistant composition of the present disclosure contains a liquid-repellent compound. The liquid-repellent compound itself may be used as the oil-resistant composition, or it may be used as the oil-resistant composition in combination with other components as described below.

[0013] The oil-resistant composition of the present disclosure is also useful as an additive for paper products, and the paper products obtained from the pulp composition added with the oil-resistant composition can have improved performance (for example, water resistance, oil resistance, paper strength, etc.).

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

[0015] The oil-resistant composition of the present disclosure can impart oil resistance to a substrate and is solid. The oil-resistant composition of the present disclosure can be provided in a solid state and does not require storage as an aqueous dispersion until use. Different from conventional aqueous dispersions, the oil-resistant composition of the present disclosure is put into a liquid medium (for example, water) at the time of use to form a dispersion. Therefore, sedimentation of the dispersed substance does not occur during storage of the oil-resistant composition of the present disclosure.

[0016] The water content of the oil-resistant agent composition of the present disclosure may be 0.01% by weight or more, 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.7% by weight or more, 1.0% by weight or more, 1.5% by weight or more, 2.0% by weight or more, 3.0% by weight or more, 3.5% by weight or more, 4.0% by weight or more, 4.5% by weight or more, or 5.0% by weight or more. The water content of the oil-resistant agent composition of the present disclosure may be 20% by weight or less, 10% by weight or less, 9.0% by weight or less, 8.0% by weight or less, 7.0% by weight or less, 6.5% by weight or less, 6.0% by weight or less, 5.5% by weight or less, or 5.0% by weight or less. The water content of the oil-resistant agent composition can be determined in accordance with the loss on drying method of JIS K0068:2001 "Methods for Measuring Water in Chemical Products".

[0017] The oil-resistant agent composition in the present disclosure may not have any selected from the group consisting of a compound having a fluoroalkyl group with 8 or more carbon atoms, a compound having a perfluoroalkyl group with 8 or more carbon atoms, a compound having a fluoroalkyl group with 4 or more carbon atoms, a compound having a perfluoroalkyl group with 4 or more carbon atoms, a compound having a perfluoroalkyl group, a compound having a fluoroalkyl group, and a compound having a fluorine atom. The oil-resistant agent composition in the present disclosure may not contain these fluorine compounds and still be able to impart liquid repellency to the substrate.

[0018] The method for measuring the particle size of the solid oil-resistant agent composition of the present disclosure may be changed according to the particle size. For example, when the oil-resistant agent composition is a powder, the average particle size of the oil-resistant agent composition can be measured by the laser diffraction scattering method. When the oil-resistant agent composition is in the form of a tablet described later, the particle size can be measured by using vernier calipers conforming to JIS B7507.

[0019] In the solid oil-resistant agent composition of the present disclosure, the volume occupancy ratio of particles of 100 μm or more measured by the laser diffraction scattering method may be 0.1% or more, 0.3% or more, 0.5% or more, 1% or more, 1.5% or more, 3% or more, 4% or more, 5% or more, or 10% or more. The volume occupancy ratio of particles of 100 μm or more measured by the laser diffraction scattering method in the oil-resistant agent composition of the present disclosure 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 setting the volume occupancy ratio of particles of 100 μm or more measured by the laser diffraction scattering method within the above range is not limited. For example, a pulverizer, a homogenizer, or the like may be used to refine the particles in the raw material and / or the dispersion liquid.

[0020] The average particle size measured by the laser diffraction scattering method in the solid oil-resistant agent composition of the present disclosure may be 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 measured by the laser diffraction scattering method in the oil-resistant agent composition of the present disclosure may be 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 the volume-based particle size distribution by the laser diffraction and scattering method. The measurement by the laser diffraction and scattering method is suitable when the oil-resistant agent composition is a powder. The "powder" means an aggregate of particles with a diameter of 3000 μm or less.

[0021] The volume fraction of particles with a size of 100 μm or more measured by the laser diffraction scattering method in the aqueous dispersion composition obtained by redispersing the oil-resistant agent 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 volume fraction of particles with a size of 100 μm or more measured by the laser diffraction scattering method in the aqueous dispersion composition obtained by redispersing the oil-resistant agent 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 setting the volume fraction of particles with a size of 100 μm or more measured by the laser diffraction scattering method within the above range is not limited. For example, the particles in the raw material and / or the dispersion liquid may be refined using a pulverizer, a homogenizer, or the like.

[0022] The average particle size measured by the laser diffraction scattering method in the aqueous dispersion composition obtained by redispersing the oil-resistant agent composition of the present disclosure in water may be 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.25 μm or more, 0.5 μm or more, 0.75 μm or more, 1 μm or more, 3 μm or more, 5 μm or more, 10 μm or more, 15 μm or more, 30 μm or more, 50 μm or more, 100 μm or more, 200 μm or more, 400 μm or more, 800 μm or more, or 1500 μm or more. The average particle size measured by the laser diffraction scattering method in the aqueous dispersion composition obtained by redispersing the oil-resistant agent composition of the present disclosure in water 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 by the laser diffraction and scattering method.

[0023] The shape of the oil-resistant agent composition of the present disclosure may be tablet-shaped. The tablet shape means a solid that retains a certain shape, for example, a lump in the form of a tablet. The shape of the tablet-shaped oil-resistant agent 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 circular cylinder, or a combination of these shapes. By being processed into a tablet shape, the handleability can be further improved.

[0024] The tablet-shaped oil-resistant agent composition may be, for example, a product obtained by compressing and molding a powdery oil-resistant agent composition. For example, the tablet-shaped oil-resistant agent composition can be a shaped body shaped to have a predetermined shape by tableting and molding at high pressure. In other words, the tablet-shaped oil-resistant agent composition can be an aggregate in which powders are solidified. The tablet-shaped oil-resistant agent composition may be produced by firing a powdery oil-resistant agent composition. Or it may be dissolved in a liquid medium or the like and molded into a predetermined shape.

[0025] When the solid oil-resistant agent composition of the present disclosure is tablet-shaped, the particle size of the oil-resistant agent composition measured by 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-resistant agent composition of the present disclosure is tablet-shaped, the particle size of the oil-resistant agent composition measured by a vernier caliper may be 500000 μm or less, 300000 μm or less, 100000 μm or less, 80000 μm or less, 70000 μm or less, 60000 μm or less, 50000 μm or less, 30000 μm or less, 10000 μm or less, 5000 μm or less, 30000 μm or less, 10000 μm or less, 5000 μm or less.

[0026] The size of the tablet-shaped oil-resistant agent composition is 10 mm 3 or more, 20 mm 3 or more, 30 mm 3 or more, 50 mm 3 or more, 70 mm 3 or more, 100 mm 3, 150 mm 3 or more, 200 mm 3 or more, 250 mm 3 or more, 300 mm 3 or more, 400 mm 3 or more, or 500 mm 3 or more, may be. The size of the tablet-shaped oil-resistant composition is 1000 mm 3 or less, 900 mm 3 or less, 800 mm 3 or less, 750 mm 3 or less, 600 mm 3 or less, 550 mm 3 or less, 500 mm 3 or less may be.

[0027] 〔Liquid-repellent compound〕 The liquid-repellent compound in the present disclosure can adhere to a substrate (particularly a pulp substrate) and impart liquid-repellent properties, such as water resistance, oil resistance, water repellency, oil repellency, and / or antifouling properties, to the substrate.

[0028] [Properties, etc.] The properties that the liquid-repellent compound may have are shown below. Such 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, 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. By having an HD contact angle of the liquid-repellent compound equal to or greater than the above lower limit, good liquid-repellent properties (particularly oil repellency) can be imparted to the substrate. The HD contact angle refers to the static contact angle of the spin-coated film of the liquid-repellent compound, and is obtained by dropping 2 μL of HD onto the spin-coated film and measuring the contact angle 1 second after droplet landing.

[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. By having a water contact angle of the liquid-repellent compound equal to or greater than the above lower limit, good liquid-repellency (particularly water repellency) can be imparted to the substrate. The water contact angle refers to the static contact angle of the liquid-repellent compound with respect to the spin-coated film, and is obtained by dropping 2 μL of water onto the spin-coated film and measuring the contact angle 1 second after the drop adheres.

[0031] The liquid-repellent compound is preferably a bio-based compound having carbon of bio-based origin. The bio-based content is measured in accordance with ASTM D6866. The bio-based content may be 20% or more, preferably 30% or more, more preferably 50% or more, still more preferably 60% or more, still more preferably 70% or more, most preferably 80% or more or 90% or more, for example 100%. A high bio-based content means that the amount of use of fossil resource-based materials typified by petroleum and the like is small, and from this perspective, it can be said that the higher the bio-based content of the liquid-repellent compound, the more preferable.

[0032] The biodegradability of the liquid-repellent compound at 180 days preferably has a biodegradability of 5% or more. Since the environmental load is reduced, the higher such biodegradability, the more preferable. The biodegradability of the liquid-repellent compound at 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, still more preferably 70% or more, and most preferably 80% or more. The biodegradability of the liquid-repellent compound at 60 days preferably has a biodegradability of 5% or more. Since the environmental load is reduced, the higher such biodegradability, the more preferable. The biodegradability of the liquid-repellent compound at 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 the biodegradability 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 may not have any selected from the group consisting of a fluoroalkyl group having 8 or more carbon atoms, a perfluoroalkyl group having 8 or more carbon atoms, a fluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group, a fluoroalkyl group, and a fluorine atom. Even if the liquid-repellent compound does not contain these fluorine-containing groups, it can impart liquid repellency to the substrate.

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

[0036] (A monovalent hydrocarbon group which may have a substituent) 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 1 to 40 carbon atoms. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and it is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be branched, cyclic or linear, and more preferably linear.

[0038] The number of carbon atoms of 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 of the hydrocarbon group may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, 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 a halogen atom, etc. (wherein R’ is, independently at each occurrence, 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 hydrocarbon group having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more. In the hydrocarbon group having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less. For example, the hydrocarbon group may have 1 to 3 (e.g., 1) -OR’ (especially -OH) as a substituent (e.g., other than at the terminal).

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

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

[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 methyl group, ethyl group, propyl group, butyl group, pentyl group, etc. (particularly aliphatic hydrocarbon groups, particularly alkyl groups, such as methyl group or ethyl group, particularly 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, 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 of 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 of the hydrocarbon group may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, more preferably 25 or less.

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

[0047] a may be 3 or more, 5 or more, 10 or more, 30 or more, 50 or more, 100 or more, 500 or more, 1000 or more, 2000 or more, or 3000 or more, preferably 10 or more. a may be 10000 or less, 7500 or less, 5000 or less, 3000 or less, 1500 or less, 1000 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less, preferably 500 or less.

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

[0049] In the polysiloxane group, R is a hydrocarbon group having 6 to 40 carbon atoms s The amount of s may be 3 mol% or more, 10 mol% or more, 20 mol% or more, or 30 mol% or more based on the total of s The amount of R which is a hydrocarbon group having 6 to 40 carbon atoms 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, R is a reactive group s The amount of s may be 5 mol% or more, 10 mol% or more, 20 mol% or more, or 30 mol% or more based on the total of s The amount of R which is a reactive group 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 group may be introduced randomly or in blocks, but it is preferably random.

[0052] The terminal structure of the polysiloxane group described above is not limited, but may be -OR s , -Si(R s )3, etc. One or more reactive groups of R s in the terminal structure may be present. 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 the linker. Such a linker is not limited, but may be a hydrocarbon group having 1 to 40 carbon atoms (for example, 1 to 20 carbon atoms) which may be interrupted by an oxygen atom, for example, a (poly)oxyalkylene group having 1 to 40 carbon atoms (for example, 1 to 20 carbon atoms).

[0054] Examples of the polysiloxane group include -[-Si(R s )2-O-] a -Si(R s )3 -L s1 -[-Si(R s )2-O-] a -Si(R s )3 -L s1 -O-L s1 -[-Si(R s )2-O-] a -R s -L s1 -[-Si(R s )2-O-] a -Si(R s )3 -L s1 -O-L s1 -[-Si(R s )2-O-] a -R s -L s1 -[-Si(R s )2-O-] a -Si(R s ) 3、 -L s1 -[-Si(R s )2-O-] a -R s [In the formula, R s is, independently at 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 in the total of the groups, 50 mol% or more is a methyl group, L s1 is a hydrocarbon group having 1 to 20 carbon atoms, a is 5 or more and 10,000 or less. ], [Chemical formula] [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. may be mentioned.

[0055] [Examples of liquid-repellent compounds] As an example of the liquid-repellent compound, a compound having a hydrocarbon group having 6 to 40 carbon atoms can be mentioned. Examples of the hydrocarbon group and preferred ranges are as described above.

[0056] As an example of the liquid-repellent compound, compounds selected from the group consisting of amine-modified products, polyol-modified products, polycarboxylic acid-modified products, and other liquid or solid oils can be mentioned (detailed 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 sulfonylurea group, a sulfonylurethane group, or a sulfonimide group (e.g., an ester group, an amide group, a urethane group, a urea group, an imide group). For example, the liquid-repellent compound may contain -C(=O)-O-, -O-C(=O)-, -C(=O)-NR'-, -O-C(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO2NR'- (R' is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms)). The liquid-repellent compound may be a compound in which a raw material compound and a modifying group (particularly a monovalent hydrocarbon group which may have the above-described substituent) are bonded via at least one of these groups. The liquid-repellent compound may contain an amide structure. By the liquid-repellent compound containing at least an amide structure, the liquid repellency can be improved. Here, the amide structure may be an amide structure in a broad sense, and may be selected from amide (acid amide) groups, urethane groups, urea groups, imide groups, thioamide groups, thiourethane groups, thiourea groups, thioimide groups, sulfonamide groups, sulfonylurethane groups, sulfonylurea 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 in the direction reversed left and right). Here, at least one of the bonds possessed by N of the amide structure may be bonded to a hydrogen atom. The amide structure is preferably -(C=O)N(-)2, and may be an amide structure in a group selected from the group consisting of an amide group, a urethane group, a urea group, and an imide group).

[0058] [Amount of liquid-repellent compound] The amount of the liquid-repellent compound 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 in the oil-resistant agent composition. The amount of the liquid-repellent compound 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 in the oil-resistant agent composition. The liquid-repellent compound alone may be used as the oil-resistant agent composition.

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

[0060] In terms of its structure, the amine-modified product in the present disclosure is excellent in dispersibility in a liquid medium, and the oil-resistant agent composition of the present disclosure can have stable performance. In the case of an oil-resistant agent composition using a polymer-type compound as an active ingredient, the molecular weight distribution is wide and it tends to contain a relatively large amount of impurity components. On the other hand, the amine-modified product can have a reduced molecular weight and a narrow (unified) molecular weight distribution, and the performance can be improved.

[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 in the present disclosure may not have an active hydrogen-containing group. Examples of the active hydrogen group-containing group include an amino group (an amino group not adjacent to a carbonyl group, for example, a primary or secondary amino group), a hydroxy group, and a carboxyl group. In particular, the amine-modified product in the present disclosure may not have a primary or secondary amino group 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 plurality of modifying groups (for example, Z N ) described below may be modified to the amine (raw material amine compound, for example, polyamine) 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 material amine compound) with a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group, which may have a substituent.

[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 alkyl group having 6 to 40 carbon atoms is modified to the amine.

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

[0067] (Amine skeleton) The amine-modified product in the present disclosure has an amine skeleton. The amine skeleton has one or more amino groups having a predetermined number of bonds (valences), which are obtained by removing a predetermined number of atoms or atomic groups (for example, hydrogen) from an amine compound. The amino group in the amine skeleton means a group selected from the group consisting of -NH2, -NH-, and -N(-)2, and also includes an amino group adjacent to a carbonyl group contained in an amide group, a urethane group, a urea group, an imide, or the like. Note that the amine skeleton may be an aliphatic group or an aromatic group having one or more amino groups, and the presence of heteroatoms other than nitrogen is not excluded.

[0068] The molecular weight of the amine skeleton may be 30 or more, 50 or more, 100 or more, 200 or more, 300 or more, 400 or more, or 500 or more. The molecular weight of the amine skeleton 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 1- to 3-valent 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, 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 (aliphatic hydrocarbon group or 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 an oxygen atom and / or a sulfur atom, or may consist only of carbon atoms, nitrogen atoms, and hydrogen atoms. The hydrocarbon group may be a hydrocarbon group interrupted by an oxygen atom and / or a sulfur atom (e.g., a chain saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 hydrocarbon aromatic rings), or a general hydrocarbon group (e.g., a chain saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 hydrocarbon aromatic rings). When the hydrocarbon group is interrupted by an oxygen atom and / or a sulfur atom, it will have an ether, thioether, polyether, or polythioether structure. The number of hydrocarbon groups possessed by 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 possessed by 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 that may be interrupted by an oxygen atom and / or a sulfur atom.

[0073] The molar ratio (C / N ratio) of carbon atoms to nitrogen atoms 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 (C / N ratio) of carbon atoms to nitrogen atoms 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, preferably 6 or less or 4 or less.

[0074] (-Y N -Z N n ) The amine-modified product in the present disclosure has the following formula: -Y N -Z N n [In the formula, Y N is a direct bond or a polyvalent group with a valence of 1 + n, Z N is a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group which may have a substituent, and n is an integer of 1 or more and 3 or less.] has 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] The number of -Y N -Z N n in the amine-modified product may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, preferably 2 or more. The number of -Y N -Z N n in the amine-modified product 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 N -Z N n in the amine-modified product is bonded to the nitrogen atom of the amine skeleton. All -Y N -Z N n among the number of, the -Y N -Z N n bonded to the nitrogen atom of the amine skeleton may account for 10% or more, 30% or more, 60% or more, 80% or more, or 100%. All -Y N -Z N n among the number of, the -Y N -Z N n bonded to the nitrogen atom of the amine skeleton may account for 75% or less, 50% or less, or 25% or less. -Y not bonded to the nitrogen atom of the amine skeleton N -Z N nIt binds to other groups (e.g., hydrocarbon groups) possessed by the amine skeleton.

[0077] (Y N ) Y N is a direct bond or a (1 + n)-valent group, preferably a (1 + n)-valent group. Y N functions as a linker connecting the amine skeleton and n Z N s.

[0078] n is the number of Z N s that bind to Y 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 aliphatic group or saturated aliphatic group) or an aromatic group.

[0080] Y N may have a molecular weight of 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more. Y 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. Y N may have one or more selected from the group consisting of an amide group, a urea group, a urethane group, and an imide group, or Y N may form one or more selected from the group consisting of an amide group, a urea group, a urethane group, and an imide together with the amino group in the amine skeleton. Examples of such amide groups, urea groups, urethane groups, and imide groups include -O-C(=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 (for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms).] Examples thereof include Y N is preferably bonded to the nitrogen atom in the amine skeleton via a -(C=O)- group.

[0082] Y N is a direct bond, -O-, -C(=O)-, -C(=NR’)-, -S-, -S(=O)2-, -C(=S)-, -NR’-, -C(OR’)R’-, -C(OR’)(-)2, -N(-)2, an aliphatic hydrocarbon group having 1 to 20 carbon atoms with a valence of 2 to 4, a hydrocarbon aromatic ring with a valence of 2 to 4, and a heterocyclic ring with a valence of 2 to 4 [In the formula, R’ is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms).] and may be a 1+n-valent group composed of one or more selected from the group consisting of

[0083] Y N is a 1+n-valent group composed of one or more selected from the group consisting of Y N1 and Y N2 and is Y N1 is a direct bond, -O-, -C(=O)-, -C(=NR’)-, -S-, -S(=O)2-, -C(=S)-, -NR’-, -C(OR’)R’-, -C(OR’)(-)2, and -N(-)2 (wherein R’ is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms)), and is a group composed of one or more selected from the group consisting of Y N2 is a group composed of one or more selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms with a valence of 2 to 4, a hydrocarbon aromatic ring with a valence of 2 to 4, and a heterocyclic ring with a valence of 2 to 4 and may be a 1+n-valent group composed of one or more selected from the group consisting of. In the present specification, Y N The group described as NIt binds to.

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

[0085] Y N1 is a direct bond or a polyvalent group. Y N1 The valence of Y may be 2 to 4, 2 to 3, or 2. N1 It 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. Y N1 The molecular weight of Y may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0087] Y N1 is composed 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’ is, in each occurrence, independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms)). Y N1 Examples of Y include a direct bond, -O-, -O-C(=O)-, -O-C(=O)-O-, -O-C(=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’ is, independently at 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).] include. Note that Y N1 When bonded to the nitrogen atom of the amine skeleton, the nitrogen atom is regarded as part of the amine skeleton (amino group).

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

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

[0090] Y N2 is a group with a valence of two or more. Y N2 The valence of may be, for example, 2 to 4, 2 to 3, or 2.

[0091] Y N2 The number of carbon atoms of 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. Y N2 The number of carbon atoms of may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[0092] Y N2It is composed of one or more selected from the group consisting of a divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a divalent to tetravalent hydrocarbon aromatic ring which may have a substituent, and a divalent to tetravalent heterocyclic ring which may have a substituent.

[0093] The divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched-chain, or straight-chain hydrocarbon group. The divalent 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 of 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 of the aliphatic hydrocarbon 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, and may be 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, etc. (wherein, R’ is independently at each occurrence 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 aliphatic hydrocarbon group having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more. In the aliphatic hydrocarbon group having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0095] Examples of the 2- to 4-valent hydrocarbon aromatic rings include groups obtained by removing 2 to 4 hydrogens 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, preferably 5 to 12. The valence of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, and may be 4 or less, 3 or less, or 2.

[0096] The hydrocarbon aromatic ring may have substituents. Examples of the substituents include -R’, -OR’, -N(R’)2, -COOR’, and halogen atoms (wherein R’ is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituents may or may not have active hydrogens. 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 hydrocarbon aromatic ring having substituents, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more. In the hydrocarbon aromatic ring having substituents, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0097] The divalent to tetravalent heterocyclic ring may be an aliphatic group or an aromatic group. Examples of the divalent to tetravalent heterocyclic ring include groups obtained by removing 2 to 4 hydrogens 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 heterocyclic ring is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valence of the heterocyclic ring may be 2 or more, 3 or more, or 4, and may be 4 or less, 3 or less, or 2.

[0098] The heterocyclic ring may have a substituent. Examples of the substituent include -R’, -OR’, -N(R’)2, -COOR’, and a halogen atom, etc. (wherein R’ is independently, in each occurrence, 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 heterocyclic ring having a substituent, 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 heterocyclic ring having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less.

[0099] Y N2 Examples of -Ali- -Cy- -Ali(-)2 -Cy(-)2 (-)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 a heterocyclic ring.] Examples thereof include the following.

[0100] Y N2 Specific examples of Y include: -(CH2) p -(where p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having an unsaturated bond and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, a hydrocarbon group having a branched structure and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH2) q -Cy-(CH2) r -(where q and r are each independently 0 to 20, for example 1 to 10, and Cy is a hydrocarbon aromatic ring or a heterocyclic ring) Examples thereof include the following.

[0101] ·Y N Examples of Y N Examples of Y will be described. In the following, R’ is, in each occurrence, independently 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 Examples of Y include, when Y N is divalent, -Y N1 -, -Y N1 -Y N2 -, -Y N1 -Y N2 -Y N1 -, -Y N1 -Y N2 -Y N1 -Y N2 -, -Y N2 -, -Y N2-Y N1 - and -Y N2 -Y N1 -Y N2 - and -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 -) 2、 -Y N1 -(Y N2 -Y N1 -Y N2 )2; -Y N2 (-)2, -Y N2 -Y N1 (-)2, -Y N2 -(Y N1 )2, -Y N2 -Y N1 -Y N2 (-)2, -Y N2 -Y N1 (-Y N2 -)2, -Y N2 -(Y N1 -Y N2 )2, -YN2 -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 N2 -Y N1 (-)3, -Y N1 -Y N2 (-Y N1 -)3, -Y N1 -(Y N2 -Y N1 -)3, -Y N1 -Y N2 -Y N1 -Y N2 (-)3, -Y N1 -Y N2 -Y N1 -(Y N2 ) 3、 -Y N1 -Y N2 -(Y N1 -Y N2 ) 3、 -Y N1 -(Y N2 -Y N1 -Y N2 )3; -Y N2 (-)3, -Y N2 -Y N1 (-)3, -Y N2 -(Y N1 )3, -YN2 -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. can be mentioned.

[0105] Y N As a preferable example 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, etc. can be mentioned. In the amine-modified product, one or more Ys N are preferably such that the terminal on the amine skeleton side is -(C=O)- and it binds to the 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 is, in each occurrence, independently, a direct bond, -O-, -O-C(=O)-, -O-C(=O)-O-, -O-C(=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)- (wherein, R' is, in each occurrence, independently, a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, 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, a divalent triazole group).] is a group represented by this. Thereby, liquid repellency can be imparted to the base material well.

[0107] Y N As further specific examples of *-(C=O)- -O-(C=O)-NR'- [In the formula, * means being bonded to the nitrogen atom of the 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). Examples thereof include the following.

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

[0109] [Examples of amine-modified products] (Example 1 of amine-modified product) Examples of the amine-modified product include 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, in each occurrence, independently a direct bond or a (1 + n)-valent group, Z N is, in each occurrence, independently a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, L 1 is, in each occurrence, independently a divalent aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms which may be interrupted by an oxygen atom and / or a sulfur atom, n is, in each occurrence, independently an integer of 1 or more and 3 or less, p is, in each occurrence, independently an integer of 0 or more and 2 or less, q is, independently in each occurrence, an integer of 0 or more and 2 or less, p + q is, for each N(-Y N -Z N n ) p (-H) q is 2, r is, independently in each occurrence, 0 or 1, s is, independently in each occurrence, 0 or 1, r + s is, for each N(-Y N -Z N n ) r (-H) s is 1, the sum of all p's and all r's is 1 or more, t is an integer of 0 or more and 10 or less.] Examples include compounds (amine-modified form 1) represented by

[0110] In amine-modified form 1, for Y N , Z N , and n, refer to the above description for details.

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

[0112] In amine modification example 1, p is, independently at each occurrence, an integer of 0 or more and 2 or less, q is, independently at each occurrence, an integer of 0 or more and 2 or less, and p + q is, for each N(-Y N -Z N n ) p (-H) q is 2. Preferably, p may be 1 or more, for example 2, independently at each occurrence.

[0113] In amine modification example 1, r is, independently at each occurrence, 0 or 1, s is, independently at each occurrence, 0 or 1, and r + s is, for each N(-Y N -Z N n ) r (-H) s is 1. Preferably, p may be 1 or more, for example 2, independently at each occurrence.

[0114] The sum of all p and all r is 1 or more, that is, amine modification example 1 has one or more -Y N -Z N n . The sum of all p and all r may be 1 or more, 3 or more, 5 or more, 7 or more, 9 or more, 12 or more (the sum of all q and all s may be 0). The sum of all p and all r may be 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, or 4 or less.

[0115] In the amine modification form 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, 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 form 2) As an example of another amine modification form, the following formula: N(-Y N -Z N n ) p (-H) q -L 2 (-Y N -Z N n ) u [In the formula, Y N is, in each occurrence, independently a direct bond or a 1 + n-valent group, Z N is, in each occurrence, independently a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, L 2 is a 1 + u-valent aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms which may be interrupted by an oxygen atom and / or a sulfur atom, n is, in each occurrence, independently an integer of 1 or more and 3 or less, p is an integer of 0 or more and 2 or less, q is an integer of 0 or more and 2 or less, p + q is 2, u is an integer of 1 or more and 3 or less, The sum of p and u is 1 or more.] Compounds (amine modification form 2) represented by the formula are exemplified.

[0117] In the amine modification form 2, for Y N , Z N and n, the above description is incorporated by reference.

[0118] In the amine modification form 2, L2 is an aliphatic hydrocarbon group or aromatic hydrocarbon group with a valence of 1+u and 2 to 20 carbon atoms, which may be interrupted by oxygen atoms and / or sulfur atoms, and may be a cyclic, branched, or linear hydrocarbon group, preferably a chain hydrocarbon group or an aromatic hydrocarbon. L 2 may refer to the hydrocarbon groups described in the above description of the [amine skeleton]. The hydrocarbon group may be interrupted by oxygen atoms and / or sulfur atoms, or may consist only of carbon atoms, nitrogen atoms, and hydrogen atoms. L 2 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. L 2 is preferably a cyclic group having both a ring (e.g., aromatic ring) and a chain structure (e.g., linear structure, ether oxygen, thioether sulfur). Specific examples include 1,3-phenylenebisalkylene group, 1,4-phenylenebisalkylene group, diphenyl ether diyl group, diphenyl thioether diyl group, etc. L 2 The carbon number of may be 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more. L 2 The carbon number of may be 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, or 3 or less.

[0119] In Amine Modification Example 2, p is an integer from 0 to 2, q is an integer from 0 to 2, and p + q is 2. Preferably, p may be 1 or more, for example, 2.

[0120] In Amine Modification Example 2, u is an integer from 1 to 3. u is 1, 2, or 3, for example, 2 or 3.

[0121] In Amine Modification Example 2, the sum of p and u is 1 or more, that is, Amine Modification Example 2 has one or more -Y N -Z N nIt has. The total of all p and u may be 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more (the total of all q may be 0). The total of p and u may be 5 or less, 4 or less, 3 or less, or 2 or less.

[0122] (Specific example) Specific examples of the amine-modified product include compounds represented by the following formula. In the following formula, Y N , Z N For details of and n, refer to the above description.

[0123]

Chemical formula

[0124]

Chemical formula

[0125]

Chemical formula

[0126]

Chemical formula

[0127]

Chemical formula

[0128]

Chemical formula

[0129]

Chemical formula

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

[0131] [Production method] The production method of the amine-modified product is not limited, but for various amines (raw material amines), in the presence of a condensing agent if necessary, Z N A method of synthesizing by reacting a carboxylic acid containing a group, a method of synthesizing by reacting an acid chloride, an acid anhydride, an isocyanate, etc. of a carboxylic acid containing a Z N group with various amines can be mentioned. The condensing agent may be a known condensing agent, and examples thereof include DCC, EDCI, CDI, BOP, COMU, DMT-MM, DPPA, Py-Bop, etc.

[0132] (Amine (raw material amine)) Examples of amines (raw material amines) that are precursors of amine skeletons include alkylamines such as methylamine, ethylamine, propylamine, butylamine, and dibutylamine that can form amine skeletons; alkylene diamines such as ethylenediamine, propylenediamine, butylenediamine, pentanediamine, hexamethylenediamine, cyclohexanediamine, and methylenebiscyclohexylamine; polyalkylene polyamines such as diethylenetriamine, triethylenetetramine, tris(2-aminoethyl)amine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tris(2-aminopropyl)amine, tetrapropylenepentamine, pentapropylenehexamine, iminobispropylamine, dibutylenetriamine, bis(2-aminoethoxy)ethane, bis(2-aminoethyl)ether, bis[2-(2-aminoethoxy)ethyl]ether, bis[2-(3-aminopropoxy)ethyl]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-aminophenanthrene, 2-, 3-, or 4-aminobiphenyl, etc.; monocyclic aromatic polyamines such as o-, m-, or p-phenylenediamine, o-, m-, or p-xylylenediamine, diaminotoluene, 2,3-, 2,4-, or 2,5-tolylenediamine, etc.;Polycyclic aromatic polyamines such as diaminobiphenyl, bisaminophenoxyphenylpropane, diaminodiphenyl ether, diaminodiphenyl sulfide, diaminodiphenyl sulfone, diaminobenzophenone, diaminodiphenylmethane, diaminophenylpropane, diaminophenylhexafluoropropane, diaminophenylphenylethane, bisaminophenoxybenzene, bisaminobenzoylbenzene, bisaminodimethylbenzylbenzene, aminophenoxybiphenyl, aminophenoxyphenyl ketone, bisaminoditrifluoromethylbenzylbenzene, aminophenoxyphenyl sulfone, aminophenoxyphenyl ether, aminophenoxyphenylpropane, bis(aminophenoxybenzoyl)benzene, bis(aminophenoxy-α,α-dimethylbenzyl)benzene, bis[(aminoaryloxy)benzoyl]diphenyl ether, bis(amino-α,α-dimethylbenzylphenoxy)benzophenone, aminophenoxyphenyl sulfide, bis[amino-α,α-dimethylbenzylphenoxy]diphenyl sulfone, 4,4'-bis[aminophenoxyphenoxy]diphenyl sulfone, diaminodiaryloxybenzophenone, diaminoaryloxybenzophenone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diaminotriphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-methylenebisaniline, 4,4'-oxydianiline, 1,3-bis(4-aminophenoxy)benzene, 4,4'-diaminodiphenyl ether, 4,4'-bis(aminophenyl)amine; 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, 4,4'-diaminodiphenyl sulfide, etc.;Examples of the hydroxyl group-containing polyamines include 2-hydroxyethyl ethylenediamine, 2-hydroxyethyl propylenediamine, di-2-hydroxyethyl ethylenediamine, di-2-hydroxyethyl propylenediamine, 2-hydroxypropyl ethylenediamine, di-2-hydroxypropyl ethylenediamine, etc. The polyamine may be a polymer obtained by polymerizing a polymerizable compound such as allylamine.;

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

[0134] [Structure, etc.] The polyol modifier 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 modifier may be 2 or more, 3 or more, 5 or more, 6 or more, preferably 7 or more, more preferably 8 or more, and still more preferably 9 or more. From the viewpoint of improving the handleability of the oil-resistant agent composition, the degree of polymerization of the polyol modifier may be 100 or less, preferably 50 or less, more preferably 30 or less, and still more preferably 15 or less. The degree of polymerization means the number of repeating monomer units constituting the polymer.;

[0135] In the present disclosure, the degree of polymerization means the average degree of polymerization. The average degree of polymerization in the present disclosure means the polymerization obtained by measuring under the following conditions.; When the polyol modifier in the present disclosure is a polyglycerol modifier obtained by modifying polyglycerol, the degree of polymerization of the polyol modifier means the average degree of polymerization of the polyglycerol. The average degree of polymerization of polyglycerol is the average degree of polymerization (n) calculated from the hydroxyl value by the end group analysis method. Specifically, the average degree of polymerization and the average molecular weight are calculated from the following formulas (Formula 1) and (Formula 2).; (Formula 1) Average molecular weight = 74n + 18 (Formula 2) Hydroxyl value = 56110(n + 2) / Average molecular weight The hydroxyl value in the above (Formula 2) is a numerical value that serves as an indicator of the number of hydroxyl groups contained in polyglycerin. The hydroxyl value is calculated from the amount of potassium hydroxide required to neutralize acetic acid necessary for acetylating the free hydroxyl groups contained in 1 g of polyglycerin, and is calculated in accordance with "Standard Oil Analysis Test Methods (I) Established by the Japan Oil Chemists' Society, 2003 Edition" compiled by the Japan Oil Chemists' Society. The hydroxyl value of the raw material polyglycerin is actually measured in accordance with the above standard oil analysis test method, and the average degree of polymerization and average molecular weight of polyglycerin can be calculated from the above relational expression.

[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 means the average degree of polymerization of the above polyvinyl alcohol. The average degree of polymerization of polyvinyl alcohol can be measured in accordance with JIS K 6726 Polyvinyl Alcohol Test Method.

[0137] When the polyol-modified product in the present disclosure is a polysaccharide-modified product obtained by modifying a polysaccharide, the degree of polymerization of the polyol-modified product means the average degree of polymerization of the above polysaccharide. The analysis of the average degree of polymerization of the polysaccharide can be performed as follows. Note that the degree of polymerization is the number of monosaccharide units (fructose and glucose units) in the polysaccharide, and the average degree of polymerization is, for example, the top of the peaks of the respective analysis results obtained by ordinary analysis methods such as HPLC, GC, and HPAEC as follows. As the column, for example, ULTRON PS-80N (8 × 300 mm) manufactured by Shinwa Chemical Industries Co., Ltd. (solvent: water, flow rate: 0.5 ml / min, temperature: 50°C) or TSK-GEL G30000 PWXL (7.8 × 300 mm) manufactured by TOSOH Corporation (solvent: water, flow rate: 0.5 ml / min, temperature: 50°C) is used, and it can be measured by using a differential refractometer as a detector.

[0138] The polyol modified product may be a low molecular weight (for example, weight average molecular weight less than 1500, less than 1000, 500 or less) and / or a 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, 100000 or more, 300000 or more, or 500000 or more. The weight average molecular weight of the polyol modified product may be 1000000 or less, 750000 or less, 500000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 10000 or less, 9000 or less, 8000 or less, 7000 or less, 6000 or less, 5000 or less, 3000 or less, 2000 or less, 1000 or less, or 500 or less.

[0139] The substitution rate of the hydroxy group 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%, preferably 10% or more, for example 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, particularly 80% or more. The substitution rate of the hydroxy group 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, for example 95% or less. Here, the "substitution rate" means the ratio (mol%) of the hydroxy groups derived from the polyol that are modified, and may mean the ratio (mol%) modified by a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group that may have a substituent.

[0140] The residual ratio of the hydroxyl groups in the polyol-modified product may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, for example, it may be 5% or more. The residual ratio of the hydroxyl groups in the polyol-modified product may be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, 15% or less, or 5% or less, for example, it may be 50% or less, 30% or less, or 10% or less. Here, the "residual ratio" means the unmodified ratio (mol%) among the hydroxyl groups derived from the polyol.

[0141] The number of modifying groups possessed by 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 possessed by 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 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 of the polyol-modified product may be 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, or 400 or less. It is the value obtained by dividing the weight average molecular weight of the polyol-modified product by the number of modifying groups. Here, the modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have a substituent.

[0143] In the polyol-modified product, one or more hydroxyl groups of the polyol are substituted by modifying groups. 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 an alkyl group having 6 to 40 carbon atoms is used to modify the polyol.

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

[0145] (-Y O -Z O n ) In the polyol-modified product of the present disclosure, one or more hydroxy groups of the polyol are substituted with a group represented by the following formula: -Y O -Z O n [wherein, Y O is a 1 + n-valent group composed of one or more selected from the group consisting of Y O1 and Y O2 , Y O1 is a group composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR’)-, -S-, -S(=O)2-, -C(=S)-, -NR’-, -C(OR’)R’-, -C(OR’)(-)2, and -N(-)2 (wherein, R’ is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms).), Y O2 is a group composed of one or more selected from the group consisting of an optionally substituted aliphatic hydrocarbon group having 2 to 4 valences and 1 to 40 carbon atoms, an optionally substituted hydrocarbon aromatic ring having 2 to 4 valences, and an optionally substituted heterocyclic ring having 2 to 4 valences, Z O is an optionally substituted monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group, n is an integer of 1 or more and 3 or less.] and may be substituted with a group represented by

[0146] (Y O ) Y O is Y O1 and YO2 a 1 + n-valent group composed of one or more selected from the group consisting of Y O1 is a group composed 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’ is, in each occurrence, independently 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).). Y O2 is a group composed of one or more selected from the group consisting of an optionally substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms and 2 to 4 valences, an optionally substituted hydrocarbon aromatic ring, and an optionally substituted heterocyclic ring having 2 to 4 valences.

[0147] n is the number of O Z that binds to Y 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 may have a molecular weight of 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more. Y 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 sulfourea group, a sulfourethane group, or a sulfonimide group. For example, Y O may contain -C(=O)-NR’-, -C(=S)-NR’-, -O-C(=O)-NR’-, -NR’-C(=O)-, -NR’-C(=O)-NR’- or -SO2NR’-. YO By containing 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 group with a valency of two or more. Y O1 The valency of Y may be 2 to 4, 2 to 3, or 2. Y O1 It 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. Y O1 The molecular weight of Y may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0153] Y O1 is composed of 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’ is, in each occurrence, independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms)). Y O1 Examples of Y include a direct bond, -O-, -O-C(=O)-, -O-C(=O)-O-, -O-C(=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’ is, independently at 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).) Examples include.

[0154] Y O1 may contain at least an amide group, urethane group, urea group, imide group, thioamide group, thiourethane group, thiourea group, thioimide group, sulfonamide group, sulfourea group, sulfourethane group, or sulfonimide group. For example, Y O2 may contain -C(=O)-NR’-, -O-C(=O)-NR’-, -NR’-C(=O)-, -NR’-C(=O)-NR’-, or -SO2NR’-. Y O1 By containing these groups, the liquid repellency can be improved.

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

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

[0157] Y O2 is a group having a valence of two or more. Y O2 The valence of may be, for example, 2 to 4, 2 to 3, or 2.

[0158] Y O2 The number of carbon atoms of 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. Y O2 The number of carbon atoms of may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[0159] Y O2 is composed of one or more selected from the group consisting of a divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a divalent to tetravalent hydrocarbon aromatic ring which may have a substituent, and a divalent to tetravalent heterocyclic ring which may have a substituent.

[0160] The divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or straight-chain hydrocarbon group. The divalent 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 of 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 of the aliphatic hydrocarbon 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, and may be 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, etc. (wherein, R’ is, independently at each occurrence, 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 aliphatic hydrocarbon group having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more. In the aliphatic hydrocarbon group having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0162] Examples of the 2- to 4-valent hydrocarbon aromatic rings include groups obtained by removing 2 to 4 hydrogens 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, preferably 5 to 12. The valence of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, and may be 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’ is, independently at each occurrence, 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 hydrocarbon aromatic ring having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more. In the hydrocarbon aromatic ring having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0164] The divalent to tetravalent heterocyclic rings may be aliphatic groups or aromatic groups. Examples of the divalent to tetravalent heterocyclic rings include groups obtained by removing 2 to 4 hydrogens 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 heterocyclic ring is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valence of the heterocyclic ring may be 2 or more, 3 or more, or 4, and may be 4 or less, 3 or less, or 2.

[0165] The heterocyclic ring may have substituents. Examples of the substituents include -R’, -OR’, -N(R’)2, -COOR’, and halogen atoms, etc. (wherein, R’ is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituents may or may not have active hydrogens. 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 heterocyclic ring having substituents, 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 heterocyclic ring having substituents, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less.

[0166] Y O2 Examples of -Ali- -Cy- -Ali(-)2 -Cy(-)2 (-)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 a heterocyclic ring.] etc. can be mentioned.

[0167] Y O2 Specific examples of −(CH2) p −(p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having an unsaturated bond with 1 to 40, 1 to 20, or 1 to 10 carbon atoms, a hydrocarbon group having a branched structure with 1 to 40, 1 to 20, or 1 to 10 carbon atoms, −(CH2) q −Cy−(CH2) r −(q and r are each independently 0 to 20, for example 1 to 10, and Cy is a hydrocarbon aromatic ring or a heterocyclic ring) etc. can be mentioned.

[0168] (Examples of Y O ) Y O Examples of will be described. In the following, R’ is, in each occurrence, independently a hydrogen atom or a hydrocarbon group having 1 to 30 (for example 1 to 20, 1 to 10, or 1 to 4) carbon atoms.

[0169] Y O Examples of are, when Y O is divalent, −Y O1 −, −Y O1 −Y O2 −, −Y O1 −Y O2 −Y O1 −, −Y O1 −Y O2 −Y O1 −Y O2 −, −Y O2 −, −Y O2-Y O1 - 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 -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] Y O As an example of Y O when it is tetravalent, -Y O1 (-)3, -Y O1 -Y O2 (-)3, -Y O1 -(Y O2 )3, -Y O1 -Y O2 -Y O1 (-)3, -Y O1 -Y O2 (-Y O1 )3, -Y O1 -(Y O2 -Y O1 )3, -Y O1 -Y O2 -Y O1 -Y O2 (-)3, -Y O1 -Y O2 -Y O1 -(Y O2 ) 3、 -Y O1 -Y O2 -(Y O1 -Y O2 ) 3、 -Y O1 -(Y O2 -Y O1 -Y O2 )3; -Y O2 (-)3, -Y O2 -Y O1 (-)3, -Y O2 -(Y O1 )3, -YO2 -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. can be mentioned.

[0172] Y O As a preferable example 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. can be mentioned.

[0173] (Preferred Y O example) Preferably, Y O is -O-Y O11 -, or -O-Y O11 -Y O21 -Y O12 - [In the formula, each symbol is independent 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-, -O-C(=O)-, -O-C(=O)-O-, -C(=O)-NR’-, -O-C(=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’-, or -C(OR’)(-)2.], may be.

[0174] Y O11 is a non-hydrocarbon linker, a direct bond or a group having a valency of 2 or more.

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

[0176] Y O11 may be a direct bond, -C(=O)-, -C(=O)-NR’-, or -C(=S)-NR’-.

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

[0178] Y O21 The number of carbon atoms of Y O21 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 of Y

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

[0180] Y O21 Specific examples of -(CH2) p -(where p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having an unsaturated bond with 1 to 40, 1 to 20, or 1 to 10 carbon atoms, a hydrocarbon group having a branched structure with 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH2) q -Cy-(CH2) r -(where q and r are each independently 0 to 20, e.g., 1 to 10, and Cy is a hydrocarbon aromatic ring or a heterocyclic ring) and the like can be mentioned.

[0181] Y O12 may be -O-, -O-C(=O)-, -O-C(=O)-O-, -O-C(=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’-, 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 sulfourea group, a sulfourethane group, or a sulfonimide group. For example, Y O12 may be -C(=O)-NR’-, -O-C(=O)-NR’-, -NR’-C(=O)-, -NR’-C(=O)-NR’- or -SO2NR’-. Y C12 By Y containing these groups, the liquid repellency can be improved.

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

[0184] [Other modifying groups] The hydroxyl group of the polyol is -Y O -Z O n may be substituted with a modifying group other than -Z. Examples of the modifying group are an anionic group and / or a cationic group.

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

[0186] Examples of the salt of the anionic group include an alkali metal salt, an alkaline earth metal salt, or an ammonium salt, such as a methylammonium salt, an ethanolammonium salt, a triethanolammonium salt and the like.

[0187] Examples of the cationic group include an amino group, preferably a tertiary amino group and a quaternary amino group. In the tertiary amino group, two groups bonded to the nitrogen atom are preferably the same or different and are an aliphatic group having 1 to 5 carbon atoms (especially an alkyl group), an aromatic group having 6 to 20 carbon atoms (aryl group) or an araliphatic group having 7 to 25 carbon atoms (especially an aralkyl group, such as a benzyl group (C6H5-CH2-)). In the quaternary amino group, three groups bonded to the nitrogen atom are preferably the same or different and are an aliphatic group having 1 to 5 carbon atoms (especially an alkyl group), an aromatic group having 6 to 20 carbon atoms (aryl group) or an araliphatic group having 7 to 25 carbon atoms (especially an aralkyl group, such as a benzyl group (C6H5-CH2-)). In the tertiary amino group and the quaternary amino group, the remaining one 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 which is a salt is a salt with an acid (organic acid or inorganic acid). Organic acids, for example, carboxylic acids having 1 to 20 carbon atoms (especially monocarboxylic acids such as acetic acid, propionic acid, butyric acid, stearic acid, etc.) are preferred.

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

[0190] (Polyol) The polyol is a compound having two or more hydroxy groups and is a compound serving as a raw material for the polyol-modified product. The 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 have a hydroxy group and an ether bond.

[0193] The polyol may be a low molecular weight (e.g., weight average molecular weight less than 1000, 500 or less) and / or a 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, 1000 or more, 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more. The weight average molecular weight of the polyol may be 1000000 or less, 750000 or less, 500000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 10000 or less, 5000 or less, 3000 or less, 2000 or less, 1000 or less, or 500 or less.

[0194] The number of hydroxy groups possessed by 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 possessed by 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 of the polyol may be 20 or more, 40 or more, 60 or more, 80 or more, 100 or more, 120 or more, 150 or more. The hydroxy group equivalent 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 of the polyol is the value obtained by dividing the weight average molecular weight of the polyol by the number of hydroxy 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 the polyol 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, xylose, etc.

[0198] Examples of oligosaccharides include sucrose, cyclodextrin, cyclomaltoheptaose, maltose, trehalose, lactose, sucralose, etc.

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

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

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

[0202] Examples of amino acids include glucosamine, etc.

[0203] Examples of vitamins include ascorbic acid, inositol, etc.

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

[0205] Examples of hydroxyhydrocarbons include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, glycerin, trimethylolpropane, trimethylolethane, etc. Hydroxyhydrocarbons are hydrocarbons having a hydroxy group, and may be aromatic or aliphatic, but are preferably aliphatic. When referring to hydroxyhydrocarbons, it may mean hydroxyhydrocarbons other than compounds included in other groups such as polysaccharides (other hydroxyhydrocarbons).

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

[0207] Examples of polyether polyols may be compounds obtained by addition polymerization of an alkylene oxide to an initiator. Examples of the initiator include compounds having two or more functional hydroxyl groups. For example, the initiator includes propylene glycol, polypropylene glycol, ethylene glycol, polyethylene glycol, glycerin, polyglycerin, trimethylolpropane, triethanolamine, pentaerythritol, ethylenediamine, aromatic diamine, diethylenetriamine, sorbitol, and sucrose (cane sugar), etc. Examples of the alkylene oxide include ethylene oxide and propylene oxide, etc. The polyether polyol obtained by addition polymerization of an alkylene oxide to the above initiator is also referred to as a polyoxyalkylene polyol or an oxyalkylene derivative of a polyol. Representative examples of polyether polyols include, for example, 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] Examples of polymer polyols are compounds obtained by polymerizing at least a part of the polyether polyol with an ethylenically unsaturated monomer in the polyether polyol. Examples of the ethylenically unsaturated monomer include acrylonitrile, styrene, and the like.

[0209] Examples of polyester polyols may be compounds obtained by dehydrative condensation of a compound having two or more functional carboxyl groups and a compound having two or more functional hydroxyl groups. Examples of the compound 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 the compound having two or more functional hydroxyl groups include ethylene glycol, propylene glycol, propanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and polymers thereof.

[0210] (Modifier) The modifier is a compound having reactivity with the polyol, and is preferably a compound having a monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a monovalent polysiloxane group as described above.

[0211] Examples of the modifier are as follows. Acid halide G(O=)C-Z O Acid anhydride O(C(=O)-Z O )2 Carboxylic acid HO(O=)C-Z O Isocyanate O=C=N-Z O Thioisocyanate S=C=N-Z O Epoxy (CH2OCH)CH2O-Z O Halide G-ZO Amine H2N-Z O Hydroxy HO-Z O [In the formula, Z O is as described above, and G is a halogen atom (for example, F, Cl, Br, or I).]

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

[0213] The polyol-modified product may be synthesized by reacting a polyol with a modifier. For example, a modifier which is an acid halide compound, an acid anhydride, or a carboxylic acid is reacted with the hydroxy group of the polyol to form an ester bond, thereby synthesizing a polyol-modified product. Further, a modifier which is a halide or an epoxy compound is reacted with the hydroxy group of the polyol to form an ether bond, thereby generating a polyol-modified product. The reaction conditions for the polyol and the modifier can be appropriately designed by those skilled in the art according to the target product, such as the use of a catalyst (for example, an acid catalyst or a base catalyst) and the use of a condensing agent.

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

[0215] [Structure, etc.] The polycarboxylic acid modified product may be a low molecule (for example, weight average molecular weight less than 1500, less than 1000, 500 or less) and / or a high molecule. The weight average molecular weight of the polycarboxylic acid modified product may be 100 or more, 200 or more, 300 or more, 400 or more, 500 or more, 1000 or more, 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more. The weight average molecular weight of the polycarboxylic acid modified product may be 1000000 or less, 750000 or less, 500000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 10000 or less, 9000 or less, 8000 or less, 7000 or less, 6000 or less, 5000 or less, 3000 or less, 2000 or less, 1000 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 according to the following apparatus and conditions. Separation column: SB-806M (8 mm×30 mm, Shodex) Column temperature: 40 °C Mobile phase solvent: Ion-exchanged water Mobile phase flow rate: 1.0 mL / min Sample concentration: 0.5 wt% Injection volume: 50 μL Detector: RI detector (Waters2414, Waters)

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

[0218] The substitution rate of the carboxyl group with a hydroxy group 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, 90% or more, or 100%, preferably 10% or more, for example, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, particularly 80% or more. The substitution rate of the carboxyl group with a hydroxy group 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, for example, 95% or less. Here, the "substitution rate" means the proportion (mol%) of the hydroxy groups of the carboxyl groups derived from the polycarboxylic acid that are modified, and may mean the proportion (mol%) modified by a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group that may have a substituent.

[0219] The remaining rate of the hydroxy group of the carboxyl group 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 remaining rate of the hydroxy group of the carboxyl group 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 "remaining rate" means the proportion (mol%) of the hydroxy groups of the carboxyl groups derived from the polycarboxylic acid that are not modified.

[0220] The number of modifying groups possessed by 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 possessed by 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 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 of the polycarboxylic acid modified product may be 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, or 400 or less. It is the value obtained by dividing the weight average molecular weight of the polycarboxylic acid modified product by the number of modifying groups. Here, the modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have a substituent.

[0222] In the polycarboxylic acid modified product, one or more hydroxy groups of the polycarboxylic acid are substituted with modifying groups. 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 with respect to the polycarboxylic acid.

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

[0224] (-Y C -Z C n ) In the polycarboxylic acid modified product in the present disclosure, the hydroxy group of one or more carboxyl groups of the polycarboxylic acid is represented by the following formula: -Y C -Z C n [wherein, Y C is a 1 + n-valent group composed of one or more selected from the group consisting of Y C1 and Y C2 and is a group represented by the formula: Y C1 is a group composed 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’ is, in each occurrence, independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms)). Y C2 is a group composed of one or more selected from the group consisting of an optionally substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms and 2 to 4 valences, an optionally substituted hydrocarbon aromatic ring, and an optionally substituted heterocyclic ring having 2 to 4 valences. Z C is an optionally substituted monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group. n is an integer of 1 or more and 3 or less.] It may be substituted by a group represented by

[0225] (Y C ) Y C is a 1 + n-valent group composed of one or more selected from the group consisting of Y C1 and Y C2 and is a group represented by the formula: Y C1 is a group composed 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’ is, in each occurrence, independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms)). Y C2is a group composed of one or more selected from the group consisting of a C1-C40 aliphatic hydrocarbon group having 2 to 4 valences which may have a substituent, a hydrocarbon aromatic ring having 2 to 4 valences which may have a substituent, and a heterocyclic ring having 2 to 4 valences which may have a substituent.

[0226] n is the number of Z C bonded to Y 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 may have a molecular weight of 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more. Y 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 sulfourea group, a sulfourethane group, or a sulfonimide group. For example, Y C may be -C(=O)-NR'-,-O-C(=O)-NR'-,-NR'-C(=O)-,-NR'-C(=O)-NR'- or -SO2NR'. Y C By containing 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 polyvalent group. The valence of Y C1 may be 2 to 4, 2 to 3, or 2. Y C1 is preferably not only a direct bond.

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

[0232] Y C1 may be composed of 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’ is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms)). Y C1 Examples of a direct bond, -O-, -O-C(=O)-, -O-C(=O)-O-, -O-C(=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. (wherein R’ is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms)). are included.

[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 sulfourea group, a sulfourethane group, or a sulfonimide group. For example, YC1 may contain -C(=O)-NR’-, -O-C(=O)-NR’-, -NR’-C(=O)-, -NR’-C(=O)-NR’- or -SO2NR’-. Y C1 By containing these groups, the liquid repellency can be improved.

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

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

[0236] Y C2 is a group having a valency of two or more. Y C2 The valency of may be, for example, 2 to 4, 2 to 3, or 2.

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

[0238] Y C2 is composed of one or more selected from the group consisting of a 2 to 4-valent aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a 2 to 4-valent hydrocarbon aromatic ring which may have a substituent, and a 2 to 4-valent heterocycle which may have a substituent.

[0239] The aliphatic hydrocarbon group having a valence of 2 to 4 and 1 to 40 carbon atoms may be a cyclic, branched, or straight-chain hydrocarbon group. The aliphatic hydrocarbon group having a valence of 2 to 4 and 1 to 40 carbon atoms may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The number of carbon atoms of 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 of the aliphatic hydrocarbon 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, and may be 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, etc. (wherein, in each occurrence, R’ 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 aliphatic hydrocarbon group having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more. In the aliphatic hydrocarbon group having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0241] Examples of the hydrocarbon aromatic ring having a valence of 2 to 4 include groups obtained by removing 2 to 4 hydrogens 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, preferably 5 to 12. The valence of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, and may be 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, etc. (wherein R’ is, independently at each occurrence, 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 hydrocarbon aromatic ring having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more. In the hydrocarbon aromatic ring having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0243] The 2- to 4-valent heterocyclic ring may be an aliphatic group or an aromatic group. Examples of the 2- to 4-valent heterocyclic ring include groups obtained by removing 2 to 4 hydrogens 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 heterocyclic ring is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valence of the heterocyclic ring may be 2 or more, 3 or more, or 4, and may be 4 or less, 3 or less, or 2.

[0244] The heterocyclic ring may have a substituent. Examples of the substituent include -R’, -OR’, -N(R’)2, -COOR’, and a halogen atom, etc. (wherein R’ is, independently at each occurrence, 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 heterocyclic ring having a substituent, 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 heterocyclic ring having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less.

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

[0246] Y C2 Specific examples of -(CH2) p -(p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having an unsaturated bond having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, A hydrocarbon group having a branched structure with carbon numbers 1 to 40, 1 to 20, or 1 to 10 -(CH2) q -Cy-(CH2) r -(q and r are each independently 0 to 20, for example 1 to 10, and Cy is a hydrocarbon aromatic ring or a heterocyclic ring) etc. can be mentioned.

[0247] (Y C example) Y C Examples of Y will be described. In the following, R’ is, in each occurrence independently, 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 Examples of Y include, when Y C is divalent, -Y C1 -, -Y C1 -Y C2 -, -Y C1 -Y C2 -Y C1 -, -Y C1 -Y C2 -Y C1 -Y C2 -, -Y C2 -, -Y C2 -Y C1 -, -Y C2 -Y C1 -Y C2 -, -Y C2 -Y C1 -Y C2 -Y C1 - etc. can be mentioned.

[0249] Y C Examples of Y include, when Y C 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 C1 -Y C2 -)2, -Y C2 -Y C1 -Y C2 -Y C1 (-)2, -Y C2 -Y C1 -Y C2 -(Y C1 -) 2、 -Y C2 -Y C1 -(Y C2 -Y C1 -) 2、 -Y C2 -(Y C1 -Y C2 -Y C1 Examples include -)2 etc.

[0250] Y C As an example of Y C when it is tetravalent, -Y C1 (-)3, -Y C1 -YC2 (-)3, -Y C1 -(Y C2 -)3, -Y C1 -Y C2 -Y C1 (-)3, -Y C1 -Y C2 (-Y C1 -)3, -Y C1 -(Y C2 -Y C1 -)3, -Y C1 -Y C2 -Y C1 -Y C2 (-)3, -Y C1 -Y C2 -Y C1 -(Y C2 -) 3、 -Y C1 -Y C2 -(Y C1 -Y C2 -) 3、 -Y C1 -(Y C2 -Y C1 -Y C2 -)3; -Y C2 (-)3, -Y C2 -Y C1 (-)3, -Y C2 -(Y C1 -)3, -Y C2 -Y C1 -Y C2 (-)3, -Y C2 -Y C1 (-Y C2 -)3, -Y C2 -(Y C1 -Y C2 -)3, -Y C2 -Y C1 -Y C2 -Y C1 (-)3, -Y C2 -Y C1 -Y C2 -(Y C1 -) 3、 -Y C2 -Y C1 -(Y C2 -Y C1 -) 3、 -Y C2 -(Y C1 -Y C2 -YC1 -), 3, etc. can be mentioned.

[0251] Y C As a preferable example 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. can be mentioned.

[0252] (Preferable Y C example) Preferably, Y C is -Y C11 - or -Y C11 -Y C21 -Y C12 - [In the formula, each symbol is independent 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-, -O-C(=O)-, -O-C(=O)-O-, -C(=O)-NR’-, -O-C(=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’-, or -C(OR’)(-)2.], may be.

[0253] Y C11is a non-hydrocarbon linker and is a direct bond or a polyvalent group.

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

[0255] Y C11 may be a direct bond, -C(=O)-, -C(=O)-NR'- or -C(=S)-NR'.

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

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

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

[0259] Y C21 Specific examples of Y include -(CH2) p -(where p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having an unsaturated bond with 1 to 40, 1 to 20, or 1 to 10 carbon atoms, a hydrocarbon group having a branched structure with 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH2) q -Cy-(CH2) r-(q and r are each independently 0 to 20, for example 1 to 10, and Cy is a hydrocarbon aromatic ring or a heterocyclic ring) etc. may be mentioned.

[0260] Y C12 may be -O-, -O-C(=O)-, -O-C(=O)-O-, -O-C(=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’-, 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 sulfourea group, a sulfourethane group, or a sulfonimide group. For example, Y C12 may be -C(=O)-NR’-, -O-C(=O)-NR’-, -NR’-C(=O)-, -NR’-C(=O)-NR’- or -SO2NR’-. Y C12 By containing these groups, the liquid repellency can be improved.

[0262] (Z C ) Z C is a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group which may have a substituent, and the descriptions in the above (monovalent hydrocarbon group which may have a substituent) and (monovalent polysiloxane group) are incorporated.

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

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

[0265] (Polycarboxylic acid) The polycarboxylic acid is a compound having two or more carboxyl groups and is a compound serving as a raw material for the polycarboxylic acid-modified product. The polycarboxylic acid is a compound having two or more carboxyl groups in the molecule. The polycarboxylic acid may be aliphatic or aromatic, but is preferably aliphatic.

[0266] The polycarboxylic acid may be low molecular weight (for example, having a weight average molecular weight of less than 1000, 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, 1000 or more, 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more. The weight average molecular weight of the polycarboxylic acid may be 1000000 or less, 7500000 or less, 500000 or less, 3000000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 10000 or less, 5000 or less, 3000 or less, 2000 or less, 1000 or less, or 500 or less.

[0267] The number of carboxyl groups of 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 of 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 of the polycarboxylic acid may be 20 or more, 40 or more, 60 or more, 80 or more, 100 or more, 120 or more, or 150 or more. The carboxyl group equivalent of the polycarboxylic acid may be 1000 or less, 800 or less, 600 or less, 400 or less, 200 or less, 100 or less, or 75 or less. The carboxyl equivalent of the polycarboxylic acid is the value obtained by dividing the weight average molecular weight of the polycarboxylic acid by the number of hydroxyl groups.

[0269] The polycarboxylic acid may be a natural product. The natural product may be a high molecular weight natural product, a low molecular weight natural product, or a derivative thereof. The above natural products also include 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] The dicarboxylic acid is a compound having 2 carboxyl groups, and examples thereof include oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, phthalic acid, terephthalic acid, malic acid, tartaric acid, aldic acid, and salts thereof.

[0272] The tricarboxylic acid is a compound having 3 carboxyl groups, and examples thereof include citric acid, tricarballylic acid, t-aconitic acid, trimellitic acid, and salts thereof.

[0273] The tetracarboxylic acid is a compound having 4 carboxyl groups, and examples thereof include pyromellitic acid and salts thereof.

[0274] The carboxyl group-containing compound polymer is a compound having 5 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 has the following formula CH2=C(-Q)-C(=O)-OH [wherein Q is a hydrogen atom, a monovalent organic group, or a halogen atom.] It may be a polymer containing a repeating unit derived from a compound represented by the formula.

[0276] Q is a hydrogen atom, a monovalent organic group, or a halogen atom excluding a fluorine atom. Q may be a hydrogen atom, a methyl group, a halogen, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. Examples of Q are 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. Q is particularly preferably a hydrogen atom.

[0277] (Modifier) The modifier is a compound having reactivity with the polycarboxylic acid, and is preferably a compound having a monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a monovalent polysiloxane group as described above.

[0278] Examples of the modifier are as follows. Epoxy (CH2OCH)CH2O-Z C Amine H2N-Z C Hydroxy HO-Z C [wherein Z C is as described above.]

[0279] In the structure of the above modifier, Z 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. For example, Z C may be -Y C -Z C n as well.

[0280] The polycarboxylic acid modified product may be synthesized by reacting a polycarboxylic acid with a modifier. For example, a modifier that is an epoxy compound can be reacted with the carboxy group of the polycarboxylic acid to form an ester bond, thereby generating a polycarboxylic acid modified product. Those skilled in the art can appropriately design the reaction conditions between the polycarboxylic acid and the modifier, such as the use of a catalyst (e.g., an acid catalyst or a base catalyst) and the use of a condensing agent, according to the target product.

[0281] [Vinyl polymer] As an example of a liquid-repellent compound, a vinyl polymer will be described. The vinyl polymer is a polymer formed by polymerizing vinyl monomers and exhibits liquid repellency.

[0282] [Properties, etc.] The vinyl polymer is preferably a compound having 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, still more preferably 60% or more, still more preferably 70% or more, most preferably 80% or more or 90% or more, for example 100%. A high biobased content means a small amount of use of fossil resource-based materials represented by petroleum and the like. From this perspective, it can be said that the higher the biobased content of the vinyl polymer, the more preferable.

[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 the 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 with 6 to 40 carbon atoms.

[0286] The hydrocarbon group of 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 is branched or linear, 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 of the hydrocarbon group may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, preferably 10 or more, 12 or more, 14 or more, or 16 or more. The number of carbon atoms of the hydrocarbon group may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, 25 or less, or 20 or less.

[0287] Monomer (a) may contain an amide group, a urea group, or a urethane group. The hydrocarbon monomer may be a combination of a hydrocarbon monomer having an amide group, a urea group, or a urethane group and a hydrocarbon monomer having no amide group, urea group, or urethane group. By including such groups in monomer (a), the effects of the present disclosure can be achieved well.

[0288] The monomer (a) having a hydrocarbon group with 6 to 40 carbon atoms is Formula: CH2=C(-X a )-C(=O)-Y a (R a ) k [In the formula, R a is 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 composed of at least one or more selected from divalent to tetravalent hydrocarbon groups having 1 carbon atom (in particular, -CH2-, -CH=), -C6H4-, -O-, -C(=O)-, -S(=O)2- or -NH- (excluding hydrocarbon groups), k is 1 to 3.] It is preferably a monomer represented by

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

[0290] Y a is a divalent to tetravalent group. Y a is preferably a divalent group. Y a is preferably a group composed of at least one or more selected from a hydrocarbon group having 1 carbon atom, -C6H4-, -O-, -C(=O)-, -S(=O)2- or -NH- (excluding hydrocarbon groups). Examples of the hydrocarbon group having 1 carbon atom include -CH2-, -CH= having a branched structure, or -C≡ having a branched structure.

[0291] Y ais -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)2-; R’ is -(CH2) m -(m is an integer of 1 to 5) or -C6H4- (a phenylene group).] may be.

[0292] Y a Specific examples of are -O-, -NH-, -O-C(=O)-, -C(=O)-NH-, -NH-C(=O)-, -O-C(=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 -O-C(=O)-, -O-(CH2) m -C(=O)-O-, -NH-(CH2) m -O-C(=O)-, -NH-(CH2) m -C(=O)-O-, -O-(CH2) m -O-C(=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 -O-C(=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 an integer of 1 to 5, particularly 2 or 4].

[0293] Y a is -O-, -NH-, -O-(CH2) m -O-C(=O)-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -O-C(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -NH-S(=O)2-, -O-(CH2) m -S(=O)2-NH-, -NH-(CH2) m -NH-S(=O)2-, or -NH-(CH2) m -S(=O)2-NH- [wherein, m is an integer of 1 to 5, particularly 2 or 4.] is preferably. Y a is -O- or -O-(CH2) m -NH-C(=O)-, particularly -O-(CH2) m 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 number of carbon atoms of the hydrocarbon group is preferably 12 to 30, for example 16 to 26 or 15 to 26, particularly 18 to 22 or 17 to 22.

[0295] Examples of monomer (a) are (a1) 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 a1 is a hydrogen atom, a monovalent organic group or a halogen atom, Y a1 is -O- or -NH-.] The monomer represented by, and (a2) formula: CH2=C(-X a2 )-C(=O)-Y a21 -Z(-Y a22 -R a2 ) n [In the formula, R a2 is 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 is each independently a group composed of at least one or more selected from a direct bond, -O-, -C(=O)-, -S(=O)2-, -NH- or -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.

[0296] (a1) Monomer 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-.] is a compound represented by.

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

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

[0299] (a2) monomer The monomer (a2) is a monomer different from the monomer (a1). The monomer (a2) is a (meth)acrylate or (meth)acrylamide having a group composed of at least one selected from -O-, -C(=O)-, -S(=O)2-, -NH- or -CH2-. The monomer (a2) has the formula: CH2=C(-X a2 )-C(=O)-Y a21 -Z(-Ya22 -R a2 ) n [wherein, R a2 is 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 is each independently a group composed of at least one selected from a direct bond, -O-, -C(=O)-, -S(=O)2-, -NH- or -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 may be a compound represented by. Y a22 and / or Z may not be a direct bond. Y a22 and Z may not be a direct bond simultaneously.

[0300] R a2 is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. R a2 In, the number of carbon atoms of the hydrocarbon group is preferably 12 to 30, such as 16 to 26 or 15 to 26, particularly 18 to 22 or 17 to 22.

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

[0302] Y a22 is -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' is independently a direct bond, -O-, -NH-, or -S(=O)2-; R' is -(CH2) m -(where m is an integer from 1 to 5), a linear hydrocarbon group having an unsaturated bond with 1 to 5 carbon atoms, a hydrocarbon group having a branched structure with 1 to 5 carbon atoms, or -(CH2) l -C6H4-(CH2) l -(where each l is independently an integer from 0 to 5 and -C6H4- is a phenylene group).] It may be.

[0303] Y a22 Specific examples of are a direct bond, -O-, -NH-, -O-C(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S(=O)2-, -S(=O)2-NH-, -O-C(=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 -O-C(=O)-, -O-(CH2) m -C(=O)-O-, -NH-(CH2) m -O-C(=O)-, -NH-(CH2) m -C(=O)-O-, -O-(CH2) m -O-C(=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 -O-C(=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 from 1 to 5.] It is.

[0304] Y a22 is preferably -O-, -NH-, -O-C(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S(=O)2-, -S(=O)2-NH-, -O-C(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C6H4. Y a22 is more preferably -NH-C(=O)-, -C(=O)-NH-, -O-C(=O)-NH-, -NH-C(=O)-O- or -NH-C(=O)-NH-. Y 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, which may have a linear structure or a branched structure. The carbon number of Z is preferably 2 to 4, particularly 2. Specific examples of Z are a direct bond, -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -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, -CH2CH2CH2CH= having a branched structure. Z may not be a direct bond.

[0306] The 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-O-C(=O)-NH-R a2 、CH2=C(-X a2 )-C(=O)-O-(CH2) m -NH-C(=O)-O-R a2 、CH2=C(-X a2 )-C(=O)-O-(CH2) m -NH-C(=O)-NH-R a2 is preferably [where R 3 and X a2 are as defined above.]. The monomer (a2) is preferably CH2=C(-X a2 )-C(=O)-O-(CH2) m -NH-C(=O)-R a2 .

[0307] The monomer (a2) can be produced by reacting a hydroxyalkyl (meth)acrylate or hydroxyalkyl (meth)acrylamide with a long-chain alkyl isocyanate. Examples of the long-chain alkyl isocyanate include lauryl isocyanate, myristyl isocyanate, cetyl isocyanate, stearyl isocyanate, oleyl isocyanate, behenyl isocyanate, and the like. Alternatively, the monomer (a2) can also 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 alkyl alcohol. Examples of the long-chain alkylamine include laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, behenylamine, and the like. Examples of the long-chain alkyl alcohol include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, and the like.

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

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[0315] The monomer (a2) has the formula: R a22 -C(=O)-NH-R a23 -O-R a21 [wherein, R a21 is 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 preferably an amide group-containing monomer represented by

[0316] R a21 is an organic residue having an ethylenically unsaturated polymerizable group and is not particularly limited if there is a double bond between carbons. Specifically, -C(=O)CR a211 =CH2, -CHR a211 =CH2, -CH2CHR a211 =CH2 and other organic residues having an ethylenically unsaturated polymerizable group are exemplified, and R a211 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Also, R 21 may have various organic groups other than the ethylenically unsaturated polymerizable group. For example, organic groups such as chain hydrocarbons, cyclic hydrocarbons, polyoxyalkylene groups, and polysiloxane groups are exemplified, and these organic groups may be substituted with various substituents. R a21 is preferably -C(=O)CR a211 =CH2.

[0317] R a22is a hydrocarbon group having 6 to 40 carbon atoms, preferably an alkyl group, and examples thereof include a chain hydrocarbon group and a cyclic hydrocarbon group. Among them, a chain hydrocarbon group is preferable, and a linear saturated hydrocarbon group is particularly preferable. R a22 has 6 to 40 carbon atoms, preferably 11 to 27, and particularly preferably 15 to 23.

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

[0319] The amide group-containing monomer may be one in which R a22 is of one type (for example, only a compound in which R a22 has 17 carbon atoms), or one in which R a22 is a combination of a plurality of types (for example, a mixture of a compound in which R a22 has 17 carbon atoms and a compound in which R a22 has 15 carbon atoms).

[0320] An example of the amide group-containing monomer is carboxylic acid amidoalkyl (meth)acrylate. Specific examples of the amide group-containing monomer include palmitic acid amide ethyl (meth)acrylate, stearic acid amide ethyl (meth)acrylate, behenic acid amide ethyl (meth)acrylate, myristic acid amide ethyl (meth)acrylate, lauric acid amide ethyl (meth)acrylate, isostearic acid ethyl amide (meth)acrylate, oleic acid ethyl amide (meth)acrylate, tertiary butyl cyclohexyl caproic acid amide ethyl (meth)acrylate, adamantane carboxylic acid ethyl amide (meth)acrylate, naphthalene carboxylic acid amide ethyl (meth)acrylate, anthracene carboxylic acid amide ethyl (meth)acrylate, palmitic acid amide propyl (meth)acrylate, stearic acid amide propyl (meth)acrylate, palmitic acid amide ethyl vinyl ether, stearic acid amide ethyl vinyl ether, palmitic acid amide ethyl allyl ether, stearic acid amide ethyl allyl ether, or a mixture thereof.

[0321] The amide group-containing monomer is preferably stearic acid amide ethyl (meth)acrylate. The amide group-containing monomer may be a mixture containing stearic acid amide ethyl (meth)acrylate. In the mixture containing stearic acid amide ethyl (meth)acrylate, the amount of stearic acid amide ethyl (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 monomer. The amount of stearic acid amide ethyl (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 monomer. The remaining monomer may be, for example, palmitic acid amide ethyl (meth)acrylate.

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

[0323] (b) Hydrophilic group-containing monomer The vinyl polymer may contain a hydrophilic group-containing monomer (b). Monomer (b) is a monomer other than monomer (a) and has a hydrophilic group. The hydrophilic group is preferably an oxyalkylene group (the alkylene group has 2 to 6 carbon atoms), particularly preferably an oxyethylene group. In particular, monomer (b) is preferably oxyalkylene (meth)acrylate, for example, polyalkylene (or monoalkylene) glycol mono(meth)acrylate and / or polyalkylene (or monoalkylene) glycol di(meth)acrylate, 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 [Wherein, X b is a hydrogen atom or a methyl group, Y b is -O- or -NH-, R b is 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)-, n is an integer from 1 to 90. ] It is preferably an oxyalkylene (meth)acrylate represented by

[0325] Examples of monomer (b) are 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) [Wherein, X b is each independently a hydrogen atom or a methyl group, A bi is each independently a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, R b is each independently an alkylene group having 2 to 6 carbon atoms, n is an integer from 1 to 90 is.] It is preferably represented by.

[0326] n may be, for example, 1 to 50, particularly 1 to 30, 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, the formula -(CH2) 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 described formula and may be random. ] may be a group represented by. -(R b O) n - In, R may be two or more (for example, 2 to 4, particularly 2), -(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, n1 and n2 are numbers of 1 or more, and the sum of n1 and n2 is 2 to 90. It may be a combination of

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

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

[0329] CH2=CHCOO-(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)O-H CH2=CH-C(=O)-NH-CH(CH3)CH2O-H CH2=CH-C(=O)-NH-CH2CH2CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH2CH(CH3)O-H 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)O-H CH2=CH-C(=O)-NH-CH2C(CH3)2O-H CH2=CH-C(=O)-NH-CH(CH2CH3)CH2O-H CH2=CH-C(=O)-NH-C(CH3)2CH2O-H CH2=CH-C(=O)-NH-CH(CH3)CH(CH3)O-H CH2=CH-C(=O)-NH-C(CH3)(CH2CH3)O-H 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)O-H 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)O-H 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)O-H 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)O-H CH2=C(CH3)-C(=O)-NH-C(CH3)(CH2CH3)O-H 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] As the monomer (b), X 2 is preferably a hydrogen atom, and is an acrylate or acrylamide. The monomer (b) is particularly preferably hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or hydroxyethyl acrylamide.

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

[0338] Examples of the monomer having an anion-donating group include monomers 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, vinyl sulfonic acid, (meth)allyl sulfonic acid, styrene sulfonic acid, phosphoric acid (meth)acrylate, vinylbenzene sulfonic acid, acrylamidotertiary butyl sulfonic acid, etc., or salts thereof.

[0339] Examples of the salt of the anion-donating group include an alkali metal salt, an alkaline earth metal salt, or an ammonium salt, such as a methylammonium salt, an ethanolammonium salt, a triethanolammonium salt, etc.

[0340] In the monomer having a cation-donating group, examples of the cation-donating group are an amino group, preferably a tertiary amino group and a quaternary amino group. In the tertiary amino group, the two groups bonded to the nitrogen atom are the same or different and are preferably an aliphatic group having 1 to 5 carbon atoms (especially an alkyl group), an aromatic group having 6 to 20 carbon atoms (aryl group), or an araliphatic group having 7 to 25 carbon atoms (especially an aralkyl group, such as a benzyl group (C6H5-CH2-)). In the quaternary amino group, the three groups bonded to the nitrogen atom are the same or different and are preferably an aliphatic group having 1 to 5 carbon atoms (especially an alkyl group), an aromatic group having 6 to 20 carbon atoms (aryl group), or an araliphatic group having 7 or more and 25 or less carbon atoms (especially an aralkyl group, such as a benzyl group (C6H5-CH2-)). In the tertiary amino group and the quaternary amino group, the remaining one group bonded to the nitrogen atom may have a carbon-carbon double bond. The cation-donating group may be in the form of a salt.

[0341] The cation-donating group which is 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 (especially monocarboxylic acids such as acetic acid, propionic acid, butyric acid, stearic acid, etc.) are preferred. Dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate and salts thereof are preferred.

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

[0343] As the monomer (c) containing an ion-donating group, methacrylic acid, acrylic acid, or dimethylaminoethyl methacrylate is preferable, and methacrylic acid or dimethylaminoethyl methacrylate is more preferable.

[0344] (d) Halogenated olefin monomer The vinyl polymer may have a repeating unit derived from the 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 substituted with 1 to 10 chlorine atoms, bromine atoms or iodine atoms. The halogenated olefin monomer (d) is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly an olefin having 2 to 5 carbon atoms and 1 to 5 chlorine atoms. Preferable specific examples of the halogenated olefin monomer (d) are vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide, vinylidene halides such as vinylidene chloride, vinylidene bromide, vinylidene iodide. Vinyl chloride or vinylidene chloride is preferable because the water repellency (particularly the durability of water repellency) is increased. The presence of the repeating unit derived from the halogenated olefin monomer (d) increases the washing durability provided by the vinyl polymer.

[0345] (e) Crosslinkable monomer The vinyl polymer, the crosslinkable monomer has at least two reactive groups and / or ethylenically unsaturated double bonds (preferably, (meth)acrylate groups), and the crosslinkable monomer (e) may be a monomer containing no fluorine atom. It may be a compound containing no 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, a carboxyl group, and the like.

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

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

[0348] Examples of the crosslinkable monomer 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, neopentyl glycol di(meth)acrylate, and the like.

[0349] (f) Monomer containing a cyclic hydrocarbon group The vinyl polymer may have a repeating unit derived from the 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 an ethylenically unsaturated double bond, and may have, for example, a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond.

[0351] The cyclic hydrocarbon group may be alicyclic or aromatic, and is preferably alicyclic. The cyclic hydrocarbon group may be saturated or unsaturated, and is preferably saturated. The cyclic hydrocarbon group may be a monocyclic group, a polycyclic group, or a bridged cyclic group, and a bridged cyclic group is preferred. The cyclic hydrocarbon group may have a chain group (for example, a linear or branched hydrocarbon group).

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

[0353] Specific examples of the cyclic hydrocarbon group include cyclohexyl group, t-butylcyclohexyl group, adamantyl group, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, bornyl group, isobornyl group, norbornyl group, dicyclopentanyl group, dicyclopentenyl group, benzyl group, phenyl group, naphthyl group, 2-t-butylphenyl group, residues obtained by removing one or more hydrogen atoms from these groups (for example, cyclohexylene group, adamantylene group, phenylene group, naphthylene group, etc.), and groups which are substituents 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, compounds obtained by substituting these acrylates with acrylamide, and the like. These may be used alone or in combination of two or more.

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

[0356] [Composition of polymer] The combination of monomers (a) to (g) constituting the repeating unit of the vinyl polymer is not particularly limited, and for example, it is as follows (parentheses 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 combinations. In the case of pulp products, it is preferable to use monomers (a), monomers (b), and monomers (c) in combination.

[0357] The amount of the repeating unit 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 the repeating unit 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 the repeating unit 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 the repeating unit derived from monomer (b) may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less based on the vinyl polymer. The amount of the repeating unit derived from monomer (b) may be 0.01 part by weight or more, 0.1 part 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 based on 100 parts by weight of the repeating unit derived from monomer (a). The amount of the repeating unit 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 based on 100 parts by weight of the repeating unit derived from monomer (a).

[0359] The amount of the repeating unit 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 the repeating unit 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 unit derived from monomer (c) may be 0.01 part by weight or more, 0.1 part 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 with respect to 100 parts by weight of the repeating unit derived from monomer (a). The amount of the repeating unit 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 with respect to 100 parts by weight of the repeating unit derived from monomer (a).

[0360] The amount of the repeating unit 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 the repeating unit derived from monomer (d) may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less based on the vinyl polymer. The amount of the repeating unit derived from monomer (d) may be 0.01 part by weight or more, 0.1 part 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 with respect to 100 parts by weight of the repeating unit derived from monomer (a). The amount of the repeating unit 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 with respect to 100 parts by weight of the repeating unit derived from monomer (a).

[0361] The amount of the repeating unit 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 with respect to the vinyl polymer. The amount of the repeating unit 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 with respect to the vinyl polymer. The amount of the repeating unit derived from monomer (e) may be 0.01 part by weight or more, 0.1 part by weight or more, 1 part by weight or more, 3 part by weight or more, 5 part by weight or more, 10 part by weight or more, 15 part by weight or more, 20 part by weight or more, 50 part by weight or more, 75 part by weight or more, 100 part by weight or more, 300 part by weight or more, 500 part by weight or more, or 1000 part by weight or more with respect to 100 parts by weight of the repeating unit derived from monomer (a). The amount of the repeating unit 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 with respect to 100 parts by weight of the repeating unit derived from monomer (a).

[0362] The amount of the repeating unit 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 with respect to the vinyl polymer. The amount of the repeating unit 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 with respect to the vinyl polymer. The amount of the repeating unit derived from monomer (f) may be 0.01 part by weight or more, 0.1 part 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 with respect to 100 parts by weight of the repeating unit derived from monomer (a). The amount of the repeating unit 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 with respect to 100 parts by weight of the repeating unit derived from monomer (a).

[0363] The amount of the repeating unit derived from the 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 the repeating unit derived from the monomer (g) may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less based on the vinyl polymer. The amount of the repeating unit derived from the monomer (g) may be 0.01 part by weight or more, 0.1 part 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 based on 100 parts by weight of the repeating unit derived from the monomer (a). The amount of the repeating unit derived from the 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 based on 100 parts by weight of the repeating unit derived from the monomer (a).

[0364] [Polymerization method] The vinyl polymer can be produced by a known polymerization method, and the conditions of the polymerization reaction can also be arbitrarily selected. Examples of such polymerization methods include solution polymerization, suspension polymerization, emulsion polymerization, and condensation polymerization.

[0365] In solution polymerization, a method is adopted in which a monomer is dissolved in an organic solvent in the presence of a polymerization initiator, and after nitrogen substitution, it is heated and stirred at 30 to 120 °C for 1 to 10 hours. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, and the like. The polymerization initiator is used in the range of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight, based on 100 parts by weight of the monomer.

[0366] The organic solvent is inert to the monomer and dissolves them. For example, esters (e.g., esters having 2 to 40 carbon atoms, specifically, ethyl acetate, butyl acetate), ketones (e.g., ketones having 2 to 40 carbon atoms, specifically, methyl ethyl ketone, diisobutyl ketone, methyl isobutyl ketone), and alcohols (e.g., alcohols having 1 to 40 carbon atoms, specifically, ethanol, butanol, isopropyl alcohol) may be used. 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, trichlorotrifluoroethane, and the like. The organic solvent is used in the range of 10 to 3000 parts by weight, for example, 50 to 2000 parts by weight, based on 100 parts by weight in total of the monomers.

[0367] In emulsion polymerization, a method is adopted in which monomers are emulsified in water in the presence of a polymerization initiator and an emulsifier, and after nitrogen substitution, they are stirred and polymerized at a temperature in the range of 50 to 80 °C for 1 to 20 hours. As the polymerization initiator, water-soluble ones such as benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, sodium peroxide, potassium persulfate, ammonium persulfate, etc., and oil-soluble ones such as azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, etc. are used. The polymerization initiator is used in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the monomers.

[0368] In order to obtain a polymer aqueous dispersion with excellent storage stability, it is desirable to polymerize the monomers after micronizing them in water using an emulsifying device capable of imparting strong crushing energy such as a high-pressure homogenizer or an ultrasonic homogenizer. Also, as the emulsifier, various anionic, cationic or nonionic emulsifiers can be used, and they are used in the range of 0.5 to 20 parts by weight based on 100 parts by weight of the monomers. It is preferable to use an anionic and / or nonionic and / or cationic emulsifier. When the monomers are not completely compatible, it is preferable to add a compatibilizer that can be sufficiently compatible with these monomers, for example, a water-soluble organic solvent or a low-molecular-weight monomer. By adding the compatibilizer, it is possible to improve the emulsifying property and copolymerizability.

[0369] As the water-soluble organic solvent, the above-described organic solvents may be used. For example, acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol, etc. may be mentioned, and it may be used in the range of 1 to 50 parts by weight, for example, 10 to 40 parts by weight with respect to 100 parts by weight of water. Further, as the low molecular weight monomer, methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, etc. may be mentioned, and it may be used in the range of 1 to 50 parts by weight, for example, 10 to 40 parts by weight with respect to 100 parts by weight of the total amount of the monomer.

[0370] In the polymerization, a chain transfer agent may be used. The molecular weight of the polymer can be changed according to the amount of the chain transfer agent used. Examples of the chain transfer agent are mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, thioglycerol (especially, (for example, having 1 to 40 carbon atoms) alkyl mercaptan), inorganic salts such as sodium hypophosphite, sodium bisulfite, etc. The amount of the 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 with respect to 100 parts by weight of the total amount of the monomer.

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

[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 (for example, having a 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 higher, 3000 or higher, 5000 or higher, 7500 or higher, 10000 or higher, 30000 or higher, 100000 or higher, 300000 or higher, or 500000 or higher, and may also be 10000000 or lower, 7500000 or lower, 5000000 or lower, 3000000 or lower, 1000000 or lower, 750000 or lower, 500000 or lower, 300000 or lower, 100000 or lower, 75000 or lower, 50000 or lower, 30000 or lower, 10000 or lower, 7500 or lower, 5000 or lower, or 3000 or lower.

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

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

[0376] [Vegetable oil and animal oil] Vegetable oil and animal oil may be liquid or solid (wax) at room temperature. Examples 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, jojoba oil, hydrogenated jojoba oil, cocoa butter, palm oil, palm kernel oil, coconut oil, rapeseed oil, hydrogenated rapeseed oil, hemp seed oil, rice oil, tea seed oil, castor oil, hydrogenated castor oil, sesame oil, fish oil, shark liver oil, squalene oil, squalene, beef tallow, lard (pork fat), mutton fat, beef foot oil, whale oil, salmon oil, bonito oil, sardine oil, cod oil, etc., and their hydrogenated oils; rice wax, carnauba wax, sunflower wax, candelilla wax, urushi wax, beeswax, lanolin, whale wax, ibota wax, etc.; 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; medium-chain triglycerides; etc.

[0377] [Dispersant] The oil-resistant 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] The dispersant may be each of an organic dispersant and an inorganic dispersant, or a combination of an organic dispersant and an inorganic dispersant.

[0379] An organic dispersant may be used as the dispersant. The organic dispersant can be classified into nonionic dispersants, anionic dispersants, cationic dispersants, and amphoteric dispersants, and the organic dispersant may mean a surfactant.

[0380] The dispersant may not contain fluorine.

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

[0382] The nonionic dispersant may be of low molecular weight or high molecular weight. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more. The molecular weight may be 100000 or less, 10000 or less, 7500 or less, 5000 or less, 25000 or less, 750 or less, or 250 or less.

[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] Examples of esters are esters of alcohols and fatty acids. Examples of alcohols are alcohols having 1 to 30 valences (especially 2 to 10 valences) and 1 to 50 carbon atoms (especially 10 to 30 carbon atoms) (for example, aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

[0386] Examples of ester ethers are compounds in which alkylene oxides (especially ethylene oxide) are added to esters of alcohols and fatty acids. Examples of alcohols are alcohols having 1 to 30 valences (especially 2 to 10 valences) and 1 to 50 carbon atoms (especially 3 to 30 carbon atoms) (for example, aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

[0387] Examples of alkanolamides are formed from fatty acids and alkanolamines. The alkanolamide may be a monoalkanolamide or a dialkanolamine. Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms. The alkanolamine may be an alkanol having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms, with 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0388] The polyol may be an alcohol having 2 to 5 valences and 10 to 30 carbon atoms. The amine oxide may be an oxide of an amine (secondary amine or preferably tertiary amine) (for example having 5 to 50 carbon atoms).

[0389] The nonionic dispersant preferably is a nonionic dispersant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms of the alkylene group in the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic dispersant generally is 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 preferably is a nonionic dispersant having an oxyalkylene group.

[0391] Nonionic dispersants may include alkylene oxide adducts of linear and / or branched aliphatic (saturated and / or unsaturated) groups, polyalkylene glycol esters of linear and / or branched fatty acids (saturated and / or unsaturated), sorbitan esters of linear and / or branched fatty acids (saturated and / or unsaturated), glycerin esters of linear and / or branched fatty acids (saturated and / or unsaturated), polyglycerin esters of linear and / or branched fatty acids (saturated and / or unsaturated), sucrose esters of linear and / or branched fatty acids (saturated and / or unsaturated), polyoxyethylene (POE) / polyoxypropylene (POP) copolymers (random copolymers or block copolymers), alkylene oxide adducts of acetylene glycols, etc. Among these, those in which the structure of the alkylene oxide adduct portion and the polyalkylene glycol portion is polyoxyethylene (POE) or polyoxypropylene (POP) or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred. Also, the nonionic dispersant may not contain an aromatic group.

[0392] The nonionic dispersant has the formula: R 1 O-(CH2CH2O) p -(R 2 O) q -R 3 [wherein R 1 is an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or an acyl group, each of R 2 is independently the same or different and is an alkylene group having 3 or more (for example, 3 to 10) carbon atoms, 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 of 2 or more, q is 0 or a number of 1 or more.] and may be a compound represented by the formula.

[0393] R 1Preferably has 8 to 20 carbon atoms, particularly preferably 10 to 18 carbon atoms. R 1 Preferred specific examples of R include an octyl group, a nonyl group, a trimethylnonyl group, a lauryl group, a tridecyl group, an oleyl group, and a stearyl group. R 2 Examples of R are a propylene group and a butylene group. In the nonionic dispersant, p may be a number of 3 or more (for example, 5 to 200). q may be a number of 2 or more (for example, 5 to 200). That is, -(R 2 O) q - may form a polyoxyalkylene chain. The nonionic dispersant may be a polyoxyethylene alkylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly, a polyoxyalkylene chain) in the center. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, a styrene chain, etc. Among them, an oxypropylene chain is preferred.

[0394] Specific examples of the nonionic dispersant include condensation products of ethylene oxide with hexylphenol, isooctylphenol, hexadecanol, oleic acid, alkane (C 12 -C 16 ) thiol, sorbitan monofatty acid (C7-C 19 ) or alkyl (C 12 -C 18 ) amine, 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 the nonionic dispersant include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene polyoxybutylene alkyl ethers, polyoxyethylene polyoxypropylene glycols, polyethyleneimine ethoxylates, 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 kind, or may be a mixture of two or more kinds. The nonionic dispersant may be a mixture of a compound having an HLB (hydrophilic-lipophilic balance) of less than 15 (particularly 5 or less) and a compound having an HLB of 15 or more. Specifically, it is preferably selected from polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene, polyoxypropylene having an HLB 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, polyoxyethylene sorbitan fatty acid esters having an HLB value of less than 7.

[0396] [Cationic dispersant] The dispersant may contain a cationic dispersant. The cationic dispersant may be a cationic surfactant. The cationic dispersant may be a compound having no amide group.

[0397] The cationic dispersant may be of a low molecular weight type (for example, having a molecular weight of 2,000 or less, particularly 10,000 or less), or may be of a high molecular weight type (for example, having a molecular weight of 2,000 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-added type ammonium salt. Specifically, amine salt type dispersants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, etc.; quaternary ammonium salt type dispersants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzalkonium chloride, benzethonium chloride, etc.; polymeric cationic dispersants such as polyquaternium-1 to 47, etc. Examples of the cationic dispersant include alkylamine salts and quaternary ammonium salts.

[0399] The low molecular weight type cationic dispersant is R 21 -N + (-R 22 )(-R 23 )(-R 24 )X - [wherein, R 21 、R 22 、R 23 and R 24 are hydrogen or a hydrocarbon group having 1 to 40 carbon atoms, and X is an anionic group.] It may be a compound represented by. R 21 、R 22 、R 23 and -R 24 Specific examples of are alkyl groups (e.g., methyl group, butyl group, stearyl group, palmityl group). Specific examples of X are halogen (e.g., chlorine), acid (e.g., hydrochloric acid, acetic acid). The cationic dispersant may be a monoalkyltrimethylammonium salt (alkyl having 4 to 40 carbon atoms).

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

[0401] Examples of the low-molecular cationic dispersant may 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 various polymers having cationic groups (for example, ammonium group, quaternary ammonium group) (for example, polyquaternium-1 to 47). Examples of the polymeric cationic dispersant include cationized starch, cationized cellulose (for example, O-(2-hydroxy-3-(trimethylammonio)propyl) hydroxyethyl cellulose chloride), cationized guar gum, cationized xanthan gum, cationized natural products such as chitosan (especially cationized saccharides); 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, quaternized vinylimidazole, and the like.

[0403] [Anionic dispersant] The dispersant may contain an anionic dispersant. The anionic dispersant may be an anionic surfactant. The dispersant may not contain an anionic dispersant.

[0404] The anionic dispersant may be of low molecular weight or high molecular weight. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more. The molecular weight may be 100000 or less, 10000 or less, 7500 or less, 5000 or less, 25000 or less, 750 or less, or 250 or less.

[0405] Examples of the anionic dispersant include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfonated fatty acid salts, N-acyl amino acid type dispersants, phosphoric acid mono- or diester type dispersants, and sulfosuccinic acid esters. As an example of the anionic dispersant, carboxylate salts (for example, fatty acid salts) and the like can be mentioned.

[0406] [Amphoteric dispersant] The dispersant may include an amphoteric dispersant. The amphoteric dispersant may be an amphoteric surfactant.

[0407] The amphoteric dispersant may be of low molecular weight or high molecular weight. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more. The molecular weight may be 100000 or less, 10000 or less, 7500 or less, 5000 or less, 25000 or less, 750 or less, or 250 or less.

[0408] Examples of the amphoteric dispersant include alanines, imidazolinium betaines, amide betaines, betaine acetate, etc. Specifically, lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylaminoacetic acid betaine, fatty acid amide propyl dimethylaminoacetic acid betaine, etc. may be mentioned.

[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 with a microscope (scanning electron microscope or transmission electron microscope). The inorganic dispersant may be hydrophilic particles.

[0411] Examples of the inorganic dispersant include polyvalent metal phosphates such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, hydroxyapatite, etc.; carbonates such as calcium carbonate, magnesium carbonate, etc.; silicates such as calcium metasilicate, etc.; sulfates such as calcium sulfate, barium sulfate, etc.; hydroxides such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, etc.

[0412] [Amount of dispersant] The amount of the dispersant may be 0.01 part by weight or more, 0.1 part 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 with respect 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 with respect to 100 parts by weight of the liquid-repellent compound.

[0413] [Excipient] The oil-resistant agent composition of the present disclosure contains an excipient. The excipient is included for the purpose of molding, increasing the amount, diluting, etc. of the oil-resistant agent composition of the present disclosure. The excipient may be at least one selected from organic excipients and inorganic excipients. Each of the organic excipient and the inorganic excipient may be used, or a combination of the organic excipient and the inorganic excipient may be used.

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

[0415] Cellulose may be cellulose nanofibers. Cellulose nanofibers are those obtained by refining raw materials of cellulose such as pulp to the nanometer level, and are fine fibers with a fiber width of about 1 to 500 nm, for example. The cellulose nanofibers may be unmodified cellulose nanofibers, or may be anionic or cationic 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 excipient] Examples of the inorganic excipient include silicic acid, silicate (e.g., calcium silicate, magnesium silicate), light anhydrous silicic acid, diatomaceous earth, zeolite, talc, vermiculite, bentonite, calcium phosphate, calcium sulfate, calcium carbonate, magnesium carbonate, and the like.

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

[0419] [Amount of excipient] The amount of the excipient may be 0.01 part by weight or more, 0.1 part by weight or more, 1 part by weight or more, 3 part by weight or more, 5 part by weight or more, 10 part by weight or more, 15 part by weight or more, 20 part by weight or more, 50 part by weight or more, 75 part by weight or more, or 100 part by weight or more with respect 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 with respect to 100 parts by weight of the liquid-repellent compound.

[0420] [Lubricant] The oil-resistant composition of the present disclosure may contain a lubricant. The lubricant adheres to the surfaces of particles such as liquid-repellent compounds, dispersants, and excipients, and the adhesive force between the particles is likely to be weakened. Therefore, it is difficult for the particles to adhere to each other and they are easily peeled off. Also, when molding the oil-resistant composition, the adhesion of the oil-resistant composition to molding equipment and the like is likely to be suppressed, which can prevent the contamination of the molding equipment. Examples of the lubricant include magnesium stearate, calcium stearate, silicic anhydride, talc, sucrose fatty acid ester, glycerin fatty acid ester, polyethylene glycol, hardened oil, sodium stearyl fumarate, and the like.

[0421] [Amount of lubricant] The amount of the lubricant may be 0.01 part by weight or more, 0.1 part by weight or more, 1 part by weight or more, 3 part by weight or more, 5 part by weight or more, 10 part by weight or more, 15 part by weight or more, 20 part by weight or more, 50 part by weight or more, 75 part by weight or more, or 100 part by weight or more with respect 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 with respect to 100 parts by weight of the liquid-repellent compound.

[0422] [Binder] The oil-resistant agent composition of the present disclosure may contain a binder. The binder can contribute to the integration of the liquid-repellent compound, the dispersant, and the excipient. In particular, when the liquid-repellent compound, the dispersant, and the excipient are powders, it facilitates the aggregation of these powders with each other and makes it easier to mold the oil-resistant agent composition. By including a binder, the strength of the oil-resistant agent composition can be improved, and it becomes easier to suppress cracking, defects, etc. of the oil-resistant agent composition during transportation. Examples of the binder include cellulose-based binders such as hydroxypropyl cellulose, hypromellose phthalate, hydroxypropyl methylcellulose acetate succinate, crystalline cellulose, powdered cellulose, low-substituted hydroxypropyl cellulose, sodium carboxymethylcellulose, ethyl cellulose, methyl cellulose, hypromellose, starch-based binders such as corn starch, potato starch, wheat starch, rice starch, partially pregelatinized starch, pregelatinized starch, silicate-based binders such as magnesium aluminometasilicate, synthetic aluminum silicate, light anhydrous silicic acid, calcium silicate, gum arabic, sodium alginate, dextrin, gelatin, pullulan, povidone, carboxyvinyl polymer, etc. Preferably, cellulose-based binders are mentioned, and particularly preferably, hydroxypropyl cellulose is mentioned.

[0423] [Amount of binder] The amount of the binder may be 0.01 part by weight or more, 0.1 part by weight or more, 1 part by weight or more, 3 part by weight or more, 5 part by weight or more, 10 part by weight or more, 15 part by weight or more, 20 part by weight or more, 50 part by weight or more, 75 part by weight or more, or 100 part by weight or more with respect 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 with respect to 100 parts by weight of the liquid-repellent compound.

[0424] [Disintegrant] The oil-resistant composition of the present disclosure may contain a disintegrant. The disintegrant is likely to take in the surrounding liquid medium. Therefore, the oil-resistant composition containing the disintegrant becomes more likely to take in the liquid medium, and it is expected that dissolution is promoted, the mechanical strength is reduced by swelling, the penetration rate into the oil-resistant composition is increased, and the oil-resistant composition is more likely to be refined in the liquid medium. When the oil-resistant composition is in tablet form (for example, a tablet), the tablet is likely to disintegrate and be coarsely granulated, and it becomes easier to efficiently prepare a dispersion of the oil-resistant composition.

[0425] Examples of the disintegrant include sodium starch glycolate, croscarmellose sodium, low-substituted hydroxypropyl cellulose, crospolyvinylpyrrolidone, carboxymethyl cellulose, carboxymethyl cellulose calcium, and the like.

[0426] [Amount of disintegrant] The amount of the disintegrant may be 0.01 part by weight or more, 0.1 part by weight or more, 1 part by weight or more, 3 part by weight or more, 5 part by weight or more, 10 part by weight or more, 15 part by weight or more, 20 part by weight or more, 50 part by weight or more, 75 part by weight or more, or 100 part by weight or more with respect 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 with respect to 100 parts by weight of the liquid-repellent compound.

[0427] [Liquid medium] The oil-resistant composition in the present disclosure may contain a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The oil-resistant composition may be a dispersion or a solution. The oil-resistant composition in the present disclosure may contain at least water.

[0428] Examples of organic solvents include esters (e.g., esters having 2 to 40 carbon atoms, specifically ethyl acetate, butyl acetate), ketones (e.g., ketones having 2 to 40 carbon atoms, specifically methyl ethyl ketone, 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, 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., alcohols, polyols such as glycol solvents, ether forms of polyols (e.g., monoether forms), 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, or 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 with respect 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 with respect 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 with respect 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 with respect 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 with respect 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 with respect to 1 part by weight of the liquid-repellent compound.

[0432] [[Silicone]] The oil-resistant agent composition in the present disclosure may contain silicone (polyorganosiloxane). By containing silicone, the liquid repellency is good.

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

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

[0435] [Amount of silicone] The amount of silicone may be 0.1 part 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 with respect 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 with respect to 100 parts by weight of the liquid-repellent compound.

[0436] [Wax] The oil-resistant agent composition in the present disclosure may contain wax. By containing wax, liquid repellency can be favorably imparted to the substrate.

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

[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 part 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 with respect 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 with respect to 100 parts by weight of the liquid-repellent compound.

[0440] [Organic acid] The oil-resistant agent composition of the present disclosure may contain an organic acid. Known organic acids can be used. Examples of the organic acid preferably include carboxylic acids, sulfonic acids, sulfinic acids, etc., and carboxylic acids are 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., and formic acid or acetic acid is particularly preferred. In the present disclosure, one kind of organic acid may be used, or two or more kinds may be used in combination.

[0441] [Amount of organic acid] The amount of organic acid may be 0.1 part 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 with respect to 100 parts by weight of the liquid-repellent compound. The amount of organic acid may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 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 with respect to 100 parts by weight of the liquid-repellent compound. The amount of organic acid may be adjusted so that the pH of the oil-resistant agent composition is 3 to 10, for example 5 to 9, particularly 6 to 8. The oil-resistant agent composition may be acidic (pH 7 or less, for example 6 or less).

[0442] [Hardening agent] The oil-resistant agent composition of the present disclosure may contain a hardening agent (active hydrogen-reactive compound or active hydrogen-containing compound).

[0443] The curing agent (crosslinking agent) in the oil-resistant agent composition can cure the liquid-repellent compound well. 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 are isocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds, and hydrazide compounds. Examples of the active hydrogen-containing compound are hydroxyl group-containing compounds, amino group-containing compounds, carboxyl group-containing compounds, ketone group-containing compounds, hydrazide compounds, and melamine compounds.

[0444] The curing agent may contain an isocyanate compound. The isocyanate compound may be a polyisocyanate compound. The polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound acts as a crosslinking agent. Examples of the polyisocyanate compound can include aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates, etc. The isocyanate compound may be a blocked isocyanate compound (for example, it may be a blocked polyisocyanate compound). The blocked isocyanate compound is a compound in which the isocyanate group of the isocyanate compound is masked with a blocking agent to suppress the reaction.

[0445] Examples of aliphatic polyisocyanates include aliphatic diisocyanates such as 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-diisocyanatomethyl 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, 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 are 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 are araliphatic diisocyanates and araliphatic triisocyanates. Specific examples of araliphatic polyisocyanates are 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 mixtures thereof, 2,4- or 2,6-tolylene diisocyanate or mixtures thereof, triphenylmethane-4,4',4''-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate, etc. These may be used alone or in combination of two or more.

[0449] Derivatives of polyisocyanates include, for example, various derivatives such as dimers, trimers, biurets, allophanates, carbodiimides, uretdiones, uretoimines, isocyanurates, iminooxadiazinediones, etc. of the above-mentioned polyisocyanate compounds. These may be used alone or in combination of two or more.

[0450] These polyisocyanates can be used singly 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 obtained by blocking the isocyanate groups of the polyisocyanate compound with a blocking agent. It is preferable to use a blocked polyisocyanate compound because it is relatively stable in solution and can be used in the same solution as the oil-resistant agent composition.

[0451] The blocking agent blocks free isocyanate groups. The blocked polyisocyanate compound can, for example, regenerate the isocyanate groups by heating to 100°C or higher, for example 130°C or higher, and can easily react with hydroxyl groups. Examples of the blocking agent are phenolic compounds, lactam compounds, aliphatic alcohol compounds, oxime compounds, etc. The polyisocyanate compound can be used alone or in combination of two or more.

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

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

[0454] [Amount of curing agent] The amount of the hardening agent may be 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more with respect to 100 parts by weight of the liquid-repellent compound. The amount of the hardening 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 with respect to 100 parts by weight of the liquid-repellent compound.

[0455] 〔Other Components〕 The oil-resistant agent composition may contain other components in addition to the above components. Examples of other components include polysaccharides, paper strength enhancers, flocculants, yield improvers, coagulants, binder resins, sizing agents, fillers, preservatives, antibacterial agents, deodorants, fragrances, and the like. These may be used alone or in combination of two or more. In addition to the above components, as other components, other water-repellent and / or oil-repellent agents, dispersants, softeners, flame retardants, paint fixatives, drying rate adjusters, cross-linking agents, film-forming aids, compatibilizers, viscosity adjusters, pH adjusters, insect repellents, defoamers, shape-retaining agents, clay, pigments, polymer dispersants, soil release agents, enzyme such as cellulase, amylase, protease, lipase, keratinase, etc. as fiber surface modifiers, antifoaming agents, etc. can be blended. These may be used alone or in combination of two or more.

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

[0457] [Paper strength enhancer, flocculant, yield improver or coagulant] Examples of paper strength enhancers, flocculants, yield improvers 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 dichloride and polyalkylene polyamines, dicyandiamide-formalin condensates, dimethyldiallylammonium chloride polymers, and olefin / maleic anhydride polymers, etc.

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

[0459] [Antistatic agent] Examples of antistatic agents include cationic antistatic agents having cationic functional groups such as quaternary ammonium salts, pyridinium salts, primary, secondary and tertiary amino groups; anionic antistatic agents having anionic functional groups such as sulfonates, sulfate esters, phosphonates, phosphate esters; amphoteric antistatic agents such as alkyl betaines and their derivatives, imidazolines and their derivatives, alanine and its derivatives; nonionic antistatic agents such as amino alcohols and their derivatives, glycerin and its derivatives, polyethylene glycol and its derivatives, etc. Ion conductive polymers obtained by polymerizing or copolymerizing monomers having these cationic, anionic and zwitterionic ion conductive groups may also be used. These may be used alone or in combination of two or more.

[0460] [Preservative agent] The preservative agent can mainly be used to enhance the antiseptic power and bactericidal power and maintain the antiseptic property during long-term storage. Examples of the preservative agent include isothiazolone-based organic sulfur compounds, benzisothiazolone-based organic sulfur compounds, benzoic acids, 2-bromo-2-nitro-1,3-propanediol, etc.

[0461] [Ultraviolet absorber] The ultraviolet absorber is a drug having the effect of protecting against ultraviolet rays, and is a component that absorbs ultraviolet rays and converts them into infrared rays, visible light, etc. and emits them. Examples of the ultraviolet absorber include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole-based compounds, 4-t-butyl-4'-methoxybenzoylmethane, etc.

[0462] [Antibacterial agent] The antibacterial agent is a component having the effect of suppressing the growth of bacteria on the fiber and further suppressing the generation of unpleasant odors derived from decomposition products of microorganisms. Examples of the antibacterial agent include cationic bactericides such as quaternary ammonium salts, zinc bis-(2-pyridylthio-1-oxide), polyhexamethylene biguanide hydrochloride, 8-hydroxyquinoline, polylysine, etc.

[0463] [Deodorant] Examples of the deodorant include cluster dextrin, methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamidopropyldimethylamine oxide, aminocarboxylic acid-based metal complexes (zinc complex of sodium methylglycine diacetate described in International Publication No. 2012 / 090580), etc.

[0464] [Amount of other components] The amount of each or the total amount of other components may be 0.1 part 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 with respect to 100 parts by weight of the liquid-repellent compound. The amount of each or the total amount of other components 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 with respect to 100 parts by weight of the liquid-repellent compound.

[0465] <Pulp composition> The pulp composition in the present disclosure contains a liquid-repellent compound and a pulp base material. The pulp composition in the present disclosure can be excellent in oil resistance and / or water resistance, preferably both.

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

[0467] The pulp composition in the present disclosure does not have to have any selected from the group consisting of a compound having a fluoroalkyl group with 8 or more carbon atoms, a compound having a perfluoroalkyl group with 8 or more carbon atoms, a compound having a fluoroalkyl group with 4 or more carbon atoms, a compound having a perfluoroalkyl group with 4 or more carbon atoms, a compound having a perfluoroalkyl group, a compound having a fluoroalkyl group, and a compound having a fluorine atom. The pulp composition in the present disclosure can impart liquid repellency to the base material 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 amounts of the respective components may be adjusted so as to obtain such a pH.

[0469] [Pulp Base Material] The pulp composition contains a pulp base material. The pulp base material is composed of pulp, and the pulp may be wood pulp, non-wood pulp, waste paper pulp, etc., and may contain at least bagasse pulp.

[0470] [Wood Pulp] Examples of wood pulp include softwood kraft pulp obtained from the genus Pinus, genus Abies, etc., and hardwood kraft pulp obtained from the genus Acacia, genus Eucalyptus, genus Fagus, genus Populus (e.g., poplar), etc. Examples of softwood kraft pulp include, for example, unbleached softwood kraft pulp (NUKP), bleached softwood pulp (NBKP), semi-bleached softwood kraft pulp (NSBKP), softwood sulfite pulp, etc. Also, examples of hardwood kraft pulp include, for example, unbleached hardwood kraft pulp (LUKP), bleached hardwood kraft pulp (LBKP), semi-bleached hardwood kraft pulp (LSBKP), hardwood sulfite pulp, etc. Note that the pulp used is used alone or in combination. In addition to kraft pulp, in addition to softwood kraft pulp and hardwood kraft pulp, there are also mechanical pulps such as stone groundwood pulp (SGP), pressure groundwood pulp (PGW), refiner groundwood pulp (RGP), thermomechanical pulp (TGP), chemigroundwood pulp (CGP), groundwood pulp (GP), thermomechanical pulp (TMP), etc. Furthermore, examples of waste paper pulp include deinked waste paper pulp, deinked and bleached waste paper pulp, or deinked, bleached, and decolorized waste paper pulp produced from tea waste paper, kraft envelope waste paper, magazine waste paper, newspaper waste paper, flyer waste paper, office waste paper, cardboard waste paper, high-quality waste paper, Kent waste paper, imitation waste paper, deed waste paper, etc.

[0471] [Non-wood Pulp] Examples of non-wood pulp include pulp obtained from bagasse, kenaf, bamboo, linters, cotton, linen, hemp, ramie, straw, esparto, manila hemp, sisal hemp, jute, flax, ganpi, mitsumata, kozo, etc. [Synthetic Fibers] The pulp composition may contain synthetic fibers. Examples of the synthetic fibers include polyamide fibers, polyester fibers typified by 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, polyimide fibers, and the like. Examples of the pulp include those obtained from bagasse and the like.

[0472] [Fiber length of pulp] 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, still more preferably 0.5 mm or more. From the viewpoint of ease of production, it is preferably 5.0 mm or less, more preferably 4.0 mm or less, still more preferably 3.0 mm or less, particularly preferably 2.0 mm or less, and most preferably 1.2 mm or less.

[0473] [Fiber width of pulp] From the viewpoint of improving oil resistance, the average fiber diameter of the pulp is preferably 5 μm or more, more preferably 10 μm or more, still more preferably 15 μm or more. Also, it is preferably 5 0 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less.

[0474] [Composition of pulp base material] When using bagasse pulp, in the pulp base material, it may be 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, preferably 20% by weight or more. Also, it may be 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 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 in the pulp base material, and may also 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 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 in the pulp base material, and may also be 99% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, or 10% by weight or less.

[0477] [Form of pulp base material] The form of the pulp base material when the liquid repellent compound is added may be pulp alone, pulp slurry, pulp products, etc. Specific examples include bleached or unbleached chemical pulps such as kraft pulp and sulfite pulp, groundwood pulp, bleached or unbleached high-yield pulps such as mechanical pulp or thermomechanical pulp, etc.; pulp slurries containing the above pulp; pulp products such as paper, paper containers, and pulp molded products.

[0478] [Amount of pulp base material] The amount of the pulp base material 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 in the pulp composition, and may also 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 is 30% by weight or less in the pulp composition, and when the pulp composition is prepared by external addition, the amount of the pulp base material may be 75% by weight or more in the pulp composition.

[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 also be 99.9% by weight or less, 95% by weight or less, 90% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, or 55% by weight or less.

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

[0481] The amount of the liquid medium 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 in the pulp composition, and may also 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 is 50% by weight or more, particularly 90% by weight or more in the pulp composition, and when the pulp composition is prepared by external addition, the amount of the liquid medium is 30% by weight or less, particularly 10% by weight or less in the pulp composition.

[0482] [Liquid-repellent compound] The pulp composition contains a liquid-repellent compound. For details on the types of liquid-repellent compounds, the description of the liquid-repellent compounds in <Oil-resistant agent composition> is incorporated 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 based on the pulp substrate, preferably 0.5% by weight or more, and may also 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 liquid-repellent compound which is an amine-modified product 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 with respect to the pulp base material, preferably 0.5% by weight or more, and may also 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.

[0485] The amount of the liquid-repellent compound which is a polyol-modified product 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 with respect to the pulp base material, preferably 0.5% by weight or more, and may also 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.

[0486] The amount of the liquid-repellent compound which is a polycarboxylic acid-modified product 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 with respect to the pulp base material, preferably 0.5% by weight or more, and may also 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.

[0487] The liquid-repellent compound may be externally added to the surface of a pulp base material (e.g., pulp products such as paper, paper containers, and pulp molded products), 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 or more, 0.03 g / m 2 or more, 0.05 g / m 2 or more, 0.1 g / m 2 or more, 0.3 g / m 2 or more, 0.5 g / m 2 or more, or 1.0 g / m 2 or more, and may be 5.0 g / m 2 or less, 4.0 g / m 2 or less, 3.0 g / m 2 or less, 2.0 g / m 2 or less, 1.0 g / m 2 or less, 0.5 g / m 2 or less, 0.3 g / m 2 or less, or 0.1 g / m 2 or less.

[0488] [Dispersant] The pulp composition may contain a dispersant. For details on the types of dispersants, refer to the description of the dispersant in <Oil-resistant agent composition>.

[0489] [Amount of dispersant] The amount of the dispersant may be 0.001 wt% or more, 0.01 wt% or more, 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 based on the pulp base material, and may also be 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, preferably 5.0 wt% or less, more preferably 3.0 wt% or less.

[0490] [Paper strengthening agent] The pulp composition may contain a paper strengthening agent. Examples of the paper strengthening agent include Polyacrylamide-based paper strengthening agents such as cationic polyacrylamide, anionic polyacrylamide, and amphoteric polyacrylamide; Starch, enzyme-modified starch, thermochemically modified starch, oxidized starch, esterified starch, etherified starch (such as hydroxyethylated starch, etc.), 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, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, chitin nanofiber, cellulose nanofiber, cellulose nanocrystal, and pullulan, polysaccharide sizing agents such as these modified polysaccharides (such as modified polysaccharides with hydroxyl groups or cationic groups introduced); Polyamide sizing agents such as polyamide resin, polyamine resin, polyamide-polyamine resin, polyamide-epichlorohydrin resin, polyamide-polyamine-epichlorohydrin resin, polyamide-polyurea-formaldehyde resin, epoxidized polyamide resin, etc.; Urea / melamine sizing agents such as urea resin, melamine resin, urea-formaldehyde resin, melamine-formaldehyde resin, etc.; Polyvinyl alcohol sizing agents such as polyvinyl alcohol, fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, ethylene-modified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, acetoacetyl group-modified polyvinyl alcohol, cation-modified polyvinyl alcohol, diacetone group-modified polyvinyl alcohol, terminal alkyl-modified polyvinyl alcohol, etc.; Examples include styrene-butadiene copolymer, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, polyacrylate ester, fatty acid diamide, polyethyleneimine resin, ketone aldehyde resin, etc. As the sizing agent in the present disclosure, polyacrylamide-based sizing agents, polysaccharide-based sizing agents, or polyamide-based sizing agents are preferred.

[0491] [Amount of sizing agent] The amount of the sizing 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 with respect to the pulp, and may also 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.

[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 sizing agents (e.g., acidic rosin sizing agents, neutral rosin sizing agents), alkyl ketene dimers, alkenyl succinic anhydrides, and the like.

[0493] [Amount of sizing agent] The amount of the 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 with respect to the pulp, and may also 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.

[0494] [Binder] The binder may include water-soluble polymers such as casein, or polyester resins, polyurethane resins, styrene-butadiene resins, vinyl acetate resins, ethylene-vinyl acetate resins, acrylonitrile-butadiene resins, polyethylene resins, polypropylene resins, carboxymethyl cellulose resins, polyamide resins, vinyl chloride resins, vinylidene chloride resins, and the like.

[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, zinc oxide, etc., and further polyenes such as polyisoprene, polychloroprene, polybutadiene, etc., polyalkenes such as polybutene, polyisobutylene, polypropylene, etc., polymers and copolymers of vinyl monomers such as vinyl acetate, styrene, (meth)acrylic acid, (meth)alkyl acrylate, (meth)acrylamide, methyl vinyl ether, etc., and various organic pigments such as solid type, hollow type, or through-hole type particles of polyurethane resin, polyester resin, polyamide resin, urea resin, melamine resin, benzoguanamine resin, etc. may be included.

[0496] 〔Other additives〕 In addition to the above, the pulp composition may also contain other additives such as fixing agents (such as sulfuric acid bands), coagulants / flocculants (such as polyamine resins), yield improvers (such as polyacrylamide resins), organic acids (such as formic acid, acetic acid), dyes, slime control agents, defoamers, polycarboxylic acids, waxes, penetrants, and other paper-making auxiliary chemicals used in the production of pulp products.

[0497] [Amount of other additives] The amount of each 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, 5% by weight or more with respect to the pulp base material, and may also 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.

[0498] Specific examples of pulp products include paper, paper containers, pulp molded products, food packaging materials, food containers, base paper for gypsum board, base paper for coating, medium-weight paper, general liners and cores, neutral pure white roll paper, neutral liners, rust-proof liners and metal laminated paper, kraft paper, neutral printing and writing paper, neutral base paper for coating, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper, and neutral information paper, etc. Examples of preferred pulp products include food packaging materials and food containers, and particularly pulp molded products for food contact applications.

[0499] <Method for producing oil-resistant agent composition> The method for producing the oil-resistant agent composition of the present disclosure is mixing a liquid-repellent compound, a dispersant, an excipient, and a liquid medium to obtain a precursor mixture, and heat-treating or drying the precursor mixture to obtain a solid oil-resistant agent composition.

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

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

[0502] From the viewpoint of performing mixing more efficiently, before mixing, the liquid-repellent compound, dispersant, and / or excipient may be pulverized by a known pulverizer such as a jet mill or a ball mill. By miniaturization, the liquid-repellent compound, dispersant, and excipient are more easily mixed uniformly.

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

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

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

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

[0507] [Molding process] In one embodiment, a molding process of molding the oil-resistant agent composition may be included. The molding process may be performed after the mixing process and before the heating process or drying process, or may be performed after the heating process or drying process.

[0508] In the molding of the oil-resistant agent composition, the oil-resistant agent composition may be molded into a tablet (pill) form. As an apparatus capable of such molding, a tableting machine may be used. That is, the oil-resistant agent composition of the present disclosure may be tableted. The type of tableting machine is not particularly limited, and a known tableting machine can be used. For example, the tableting machine is a single-shot tableting machine that compresses and forms the oil-resistant agent composition filled in a mortar by a pair of upper and lower pestles to produce tablets, or on the outer periphery of a horizontally rotating turntable, mortars are embedded at equal intervals, and a rotary tableting machine that continuously performs a series of operations of filling, compressing, and discharging the oil-resistant agent composition while the turntable rotates can be used.

[0509] In the molding of the oil-resistant agent composition, the solid oil-resistant composition obtained by heat treatment or drying treatment may be crushed or pulverized. Although the crushed or pulverized product has an irregular shape, it is not necessary to mold the oil-resistant composition of the present disclosure into a specific shape, and the production efficiency is good when it is desired to adjust it to have a size below a predetermined size. Crushing or pulverization may be performed by a known crusher or pulverizer.

[0510] <Method for manufacturing a treated fiber product or paper product> The method for manufacturing a product treated with the oil-resistant agent composition in the present disclosure includes a treatment step of treating a substrate with the above-described oil-resistant agent composition.

[0511] "Treatment" means applying the oil-resistant agent composition to a substrate by dipping, spraying, coating, etc. By the treatment, the liquid-repellent compound, which is the active ingredient of the oil-resistant agent composition, adheres to the inside and / or surface of the substrate. Here, the adhesion may be physical adhesion or chemical adhesion. For example, the liquid-repellent compound may be physically or (reactively) chemically modified to the hydroxyl groups of the substrate (fiber, paper, glass, etc.).

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

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

[0514] Examples of the substrate of the fiber product include animal and plant natural fibers 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 a mixed fiber thereof. Fiber products include woven fabrics, knitted fabrics, and non-woven fabrics, fabrics in the form of clothing (e.g., water-repellent clothing, e.g., raincoats), and carpets. However, the fibers, yarns, and intermediate fiber products (e.g., sliver or roving, etc.) in the state before being made into a fabric may be treated.

[0515] Examples of the substrate of the paper product 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, waste paper pulp such as newspaper waste paper, magazine waste paper, cardboard waste paper, or deinked waste paper, paper containers made of paper, molded bodies made of paper, etc. Specific examples of paper products include food packaging materials, food containers, base paper for gypsum board, coated base paper, medium paper, general liners and cores, neutral pure white roll paper, neutral liners, rust-proof liners and metal laminated 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, mold paper (mold containers), etc. Preferred examples include food packaging materials and food containers.

[0516] The base materials treated with the oil-resistant agent composition of the present disclosure are not limited to fiber products or paper products, and other examples include stone, filters (e.g., electrostatic filters), dust masks, parts of fuel cells (e.g., gas diffusion electrodes and gas diffusion supports), glass, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plasters, etc.

[0517] When the base material is glass, the manufactured glass product may be an optical member. Some layer (or film), such as a hard coat layer or an antireflection layer, etc., may be formed on the surface (outermost layer) of the glass base material. Either a single-layer antireflection layer or a multilayer antireflection layer may be used for the antireflection layer. Examples of inorganic substances that can be used for the antireflection layer include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, CeO2, MgO, Y2O3, SnO2, MgF2, WO3, etc. These inorganic substances may be used alone or in combination of two or more of them (e.g., as a mixture). When forming a multilayer antireflection layer, it is preferable to use SiO2 and / or SiO for its outermost layer. When the article to be manufactured is an optical glass component for a touch panel, a thin film using a transparent electrode, such as indium tin oxide (ITO) or indium zinc oxide, etc., may be provided on a part of the surface of the base material (glass). Also, depending on its specific specifications, etc., the base material may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), a fogging film layer, a hard coating film layer, a polarizing film, a retardation film, and a liquid crystal display module, etc.

[0518] [Treatment method] The oil-resistant agent composition of the present disclosure can be applied to a substrate by a conventionally known method as a treatment agent (particularly a surface treatment agent). As a treatment method, the oil-resistant agent composition in the present disclosure may be dispersed and diluted in an organic solvent or water if necessary, and adhered to the inside and / or surface of the substrate by a known method such as dipping coating, spray coating, foam coating, etc., and then dried. After drying, a fiber product with the solid component in the oil-resistant agent composition adhered thereto can be obtained. Further, if necessary, it may be applied together with a suitable crosslinking agent and cured. To the oil-resistant agent composition of the present disclosure, if necessary, further, a water and / or oil repellent, an anti-slip agent, an antistatic agent, a handle modifier, a softener, an antibacterial agent, a flame retardant, a paint fixing agent, an anti-wrinkle agent, a drying rate adjuster, a crosslinking agent, a film-forming aid, a compatibilizer, an antifreezing agent, a viscosity adjuster, an ultraviolet absorber, an antioxidant, a pH adjuster, an insect repellent, an antifoaming agent, and other various additives can also be used in combination. Examples of the various additives may be the same as those described in "other components" in the above description. The concentration of the oil-resistant agent composition in the treatment agent in contact with the substrate may be appropriately changed depending on the application, but may be 0.01 to 10% by weight, for example, 0.05 to 5% by weight.

[0519] The oil-resistant agent composition can be applied to the substrate by any of the methods known for treating the substrate with a liquid. The substrate may be immersed in the oil-resistant agent composition, or a solution may be adhered or sprayed onto the substrate. The treated substrate is preferably dried and cured by heating in order to exhibit 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 also be obtained with low-temperature heating (for example, 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 fiber product is paper, it may be coated on the paper, or a solution may be adhered or sprayed onto the paper, or it may be treated by mixing with the pulp slurry before papermaking. The treatment may be an external addition treatment or an internal addition treatment. Alternatively, the oil-resistant agent composition may be applied to the fiber product by a cleaning method, for example, applied to the fiber product in a washing application or a dry cleaning method, etc.

[0520] [Treatment of paper products] Examples of the paper substrate include paper, paper-made containers, and paper-made molded articles (e.g., pulp moldings).

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

[0522] Since the oil-resistant agent composition of the present disclosure is solid, before treating paper with the oil-resistant agent composition of the present disclosure, the oil-resistant agent composition of the present disclosure is dispersed in a liquid medium. Since the oil-resistant agent composition of the present disclosure contains a dispersant, a dispersion of the oil-resistant agent composition (e.g., an aqueous dispersion) can be obtained by adding it to the liquid medium. From the viewpoint of more efficiently preparing the dispersion, after adding the oil-resistant agent composition to the liquid medium, it may be stirred for a predetermined time. As the liquid medium, the liquid medium of the present disclosure can be used, and for example, water can be used.

[0523] The amount of the oil-resistant agent composition in the dispersion of the oil-resistant agent composition of the present disclosure is 1% by weight or more, 3% by weight or more, 5% by weight or more, 7% by weight or more, 10% by weight or more, 15% by weight or more, 20% by weight or more, or 25% by weight or more. The amount of the oil-resistant agent composition in the dispersion of the oil-resistant 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.

[0524] The amount of the liquid-repellent compound in the dispersion of the oil-resistant agent composition of the present disclosure is 1% by weight or more, 3% by weight or more, 5% by weight or more, 7% by weight or more, 10% by weight or more, 15% by weight or more, 20% by weight or more, or 25% by weight or more. The amount of the liquid-repellent compound in the dispersion of the oil-resistant 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 manufactured by a conventionally known papermaking method. An internal addition treatment method of adding an oil-resistant agent composition to the pulp slurry before papermaking or an external addition treatment method of applying the oil-resistant agent composition to the paper after papermaking can be used.

[0526] The size press of the external addition treatment method can also be classified as follows according to the coating method. One coating method is a so-called pond-type two-roll size press in which a coating liquid (sizing liquid) is supplied to a nip portion formed by passing the paper between two rubber rolls to create a coating liquid reservoir called a pond, and the sizing liquid is applied to both sides of the paper by passing the paper through this coating liquid reservoir. The other coating methods are a gate roll type in which the sizing liquid is applied by a surface transfer type and a rod metering size press. In the pond-type two-roll size press, the sizing liquid easily penetrates into the interior of the paper, and in the surface transfer type, the sizing liquid components tend to remain on the surface of the paper. The surface transfer type has a coating layer that tends to remain on the surface of the paper and has a larger coating layer formed on the surface than the pond-type two-roll size press. In the present disclosure, the performance can be imparted to the paper even when the former pond-type two-roll size press is used. The paper treated in this way can exhibit excellent oil resistance and water resistance, etc. by optionally undergoing a heat treatment in a temperature range up to 300°C, for example up to 200°C, particularly 80°C to 180°C, depending on the properties of the paper, after simple drying at room temperature or high temperature.

[0527] The internal addition treatment method may mean a treatment method of adding an oil-resistant agent composition to the pulp slurry before papermaking. As the internal addition treatment method, pulp molded products can be manufactured by filling a mold with a pulp slurry added with an oil-resistant agent composition and permeating water outside the mold to form the pulp. Specifically, it may include one or more of the steps of adding an aqueous dispersion of an oil-resistant agent composition to the pulp slurry and stirring and mixing, suction-dehydrating the pulp composition prepared in this step through a reticulate body of a predetermined shape to deposit the pulp composition to form an intermediate pulp mold, and molding and drying the intermediate pulp mold with a heated molding die to obtain a pulp molded product, specifically, paper, a container made of paper, or a molded body made of paper, but is not limited thereto. Examples of the method of permeating water in the pulp slurry outside the mold include a method of naturally permeating water at normal pressure and a method of forcibly permeating water by reducing the pressure outside the mold. The treated paper may optionally be heat-treated depending on the properties of the paper after simple drying at room temperature or high temperature. 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 particularly may be in the range of 80°C to 180°C. By performing the heat treatment within such a temperature range, excellent oil resistance and water resistance can be exhibited.

[0528] The present disclosure can be used in gypsum board base paper, coated base paper, medium paper, general liner and core, neutral pure white roll paper, neutral liner, rust-proof liner and metal laminated 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] As the pulp raw material, bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, groundwood pulp, mechanical pulp or thermomechanical pulp, etc. Any of bleached or unbleached high-yield pulp, waste newsprint, waste magazines, corrugated cardboard waste, or deinked waste paper can be used. Also, a mixture of the above pulp raw materials and synthetic fibers such as asbestos, polyamide, polyimide, polyester, polyolefin, and polyvinyl alcohol can be used.

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

[0531] If necessary, for the paper, as papermaking chemicals used to a normal extent, paper strength enhancers such as starch, modified starch, carboxymethyl cellulose, polyamide polyamine-epichlorohydrin resin, flocculants, fixing agents, yield improvers, dyes, fluorescent dyes, slime control agents, defoamers, and other additives used in the manufacture of paper can be used. It is preferable to use starch and modified starch. If necessary, an oil-resistant agent composition can be applied to the paper by a size press, a gate roll coater, a blade coater, a calender, etc. using starch, polyvinyl alcohol, dyes, coating colors, anti-slip agents, etc.

[0532] In the case of external addition, the amount of the liquid-repellent compound contained in the coating layer is 0.01 to 2.0 g / m 2 、particularly preferably 0.1 to 1.0 g / m 2 . The coating layer is preferably formed of an oil-resistant agent composition, starch, and / or modified starch. The solid content of the oil-resistant agent composition for paper in the coating layer is preferably 2 g / m 2 or less. In the case of internal addition, it is preferable to mix the oil-resistant agent composition with the pulp such that the amount of the oil-resistant agent 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, based on 100 parts by weight of the pulp forming the paper.

[0533] In external addition, a treatment liquid is stored between rolls, and the base paper is passed through the treatment liquid between the rolls at an arbitrary roll speed and nip pressure, and oil resistance can be imparted to the paper even by using a so-called pond type two-roll size press treatment.

[0534] In the external addition treatment, the paper base material may contain additives such as sizing agents, paper strength enhancers, flocculants, retention aids or coagulants. The additives may be nonionic, cationic, anionic or amphoteric. The ionic charge density of the additives is -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 (solid content or active ingredient) such as sizing agents, paper strength enhancers, flocculants, retention aids or coagulants can generally be used in an amount of 0.1 to 10% by weight (for example, 0.2 to 5.0% by weight) based on the pulp. In the case of a paper base material containing a cationic additive (for example, a sizing agent, a paper strength enhancer, a flocculant, a retention aid or a coagulant), the oil resistance composition is preferably anionic.

[0535] In the internal addition treatment, it is preferable to form paper from a pulp slurry having a pulp concentration of 0.5 to 5.0% by weight (for example, 2.5 to 4.0% by weight). Additives (for example, sizing agents, paper strength enhancers, flocculants, retention aids or coagulants, etc.) and liquid repellent compounds can be added to the pulp slurry. Examples of the additives (for example, sizing agents, paper strength enhancers, flocculants, retention aids or coagulants, etc.) are alkyl ketene dimer, alkenyl succinic anhydride, styrene-based polymers (styrene / maleic acid-based polymers, styrene / acrylic acid-based polymers), urea-formaldehyde polymers, polyethyleneimine, melamine-formaldehyde polymers, polyamideamine-epichlorohydrin polymers, polyacrylamide-based polymers, polyamine-based polymers, polydiallyldimethylammonium chloride, alkylamine·epichlorohydrin condensates, condensates of alkylene dichloride and polyalkylene polyamines, dicyandiamide·formalin condensates, dimethyldiallylammonium chloride polymers, olefin / maleic anhydride polymers.

[0536] [Pretreatment of Fiber Products] The fiber product may be pretreated before being treated with the oil-resistant agent composition of the present disclosure. By performing the pretreatment of the fiber product, excellent fastness can be imparted to the fiber product after treatment with the oil-resistant agent composition.

[0537] Examples of the pretreatment of the fiber product include cationization treatment by reaction with a reactive quaternary ammonium salt, anionic treatment such as sulfonation, carboxylation, phosphorylation, etc., acetylation treatment, benzoylation treatment, carboxymethylation treatment, grafting treatment, tannic acid treatment, polymer coating treatment, etc. after the anionic treatment.

[0538] As a method for pretreating the fiber product, although not limited, the fiber product can be pretreated by a conventionally known method. The pretreatment liquid can be dispersed and diluted in an organic solvent or water as necessary, and attached to the inside and / or surface of the fiber product by a known method such as immersion coating, spray coating, foam coating, etc., and then dried. The pH and temperature of the pretreatment liquid may be adjusted according to the required degree of treatment. As an example of the method for pretreating the fiber product, the method for pretreating the fiber product with the above-mentioned treatment agent will be described in detail.

[0539] The pretreatment method of the fiber product is to introduce -SO3M 1 (wherein M 1 represents a monovalent cation), -COOM 2 (wherein M 2 represents a monovalent cation), and -O-P(O)(OX 1 )(OX 2 (wherein X 1 and X 2 each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms)) (hereinafter, may also be referred to as "specific functional group") from the group consisting of one or more functional groups selected.

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

[0541] The fiber containing the above specific functional group (hereinafter sometimes referred to as "functional group-containing fiber") can be prepared, for example, by the following method. (i) A compound having the above specific functional group is attached to the fiber material. Note that the attachment of the compound may be in a state where a part of the compound and a part of the fiber are chemically bonded within a range where a sufficient amount of the above specific functional group remains. (ii) A fiber in which the above specific functional group is directly introduced into the material constituting the fiber is prepared.

[0542] In the case of (i), for example, a functional group-containing fiber can be obtained by a functional group introduction step of treating the fiber material with a pretreatment liquid containing one or more compounds having the above specific functional group.

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

[0544] In the present embodiment, from the viewpoint of improving the water repellency of the obtained fiber product, it is preferable to use a fiber material containing polyamide and polyester as materials, and particularly, nylon such as nylon 6 and nylon 6,6, polyester such as polyethylene terephthalate (PET), polytrimethyl terephthalate, and polylactic acid, and mixed fibers containing these are preferably used.

[0545] The above -SO3M 1As the compound having [a certain group], a phenolic polymer can be used. Examples of such phenolic polymers include those containing at least one compound represented by the following general formula.

[0546] [Chemical formula] [In the formula, X 2 is -SO3M 3 (wherein 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] [Chemical formula] [In the formula, M 4 represents a monovalent cation.]

[0548] As the above M 3 , examples include H, K, Na, or an ammonium ion which may have a substituent.

[0549] As the above M 4 , examples include H, K, Na, or 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] As the compound having the above -COOM 2 , examples include polycarboxylic acid-based polymers.

[0552] As the polycarboxylic acid-based polymer, for example, a polymer synthesized by a conventionally known radical polymerization method using acrylic acid, methacrylic acid, maleic acid, etc. as monomers, or a commercially available product can be used.

[0553] Examples of the method for producing the polycarboxylic acid polymer include a method in which a radical polymerization initiator is added to an aqueous solution of the above monomer and / or its salt, and the mixture is heated and reacted at 30 to 150 °C for 2 to 5 hours. At this time, alcohols such as methanol, ethanol, and isopropyl alcohol, or aqueous solvents such as acetone may be added to the aqueous solution of the above monomer and / or its salt. Examples of the radical polymerization initiator include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, redox polymerization initiators formed by combinations of persulfates and sodium bisulfite, hydrogen peroxide, water-soluble azo polymerization initiators, and the like. These radical polymerization initiators may be used alone or in combination of two or more. Further, a chain transfer agent (for example, octyl thioglycolate) may be added for the purpose of adjusting the degree of polymerization during radical polymerization.

[0554] In radical polymerization, a monomer copolymerizable with the above monomer can be used in addition to the above monomer. Examples of the copolymerizable monomer include v...

Claims

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

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

4. The liquid-repellent compound is selected from the group consisting of an amine-modified product, a polyol-modified product, and a polycarboxylic acid-modified product, wherein the amine-modified product has an amine skeleton and the following formula: -Y Ｎ -Z Ｎ ｎ [Y Ｎ is a 1 + n-valent group composed of one or more selected from the group consisting of Y Ｎ１ and Y Ｎ２ and is a 1 + n-valent group composed of one or more selected from the group consisting of Y Ｎ１ is a group composed of one or more selected from the group consisting of 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, in each occurrence, independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms). Y Ｎ２ is a group composed of one or more selected from the group consisting of a divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a divalent to tetravalent hydrocarbon aromatic ring which may have a substituent, and a divalent to tetravalent heterocyclic ring which may have a substituent. Z Ｎ is a monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a monovalent polysiloxane group, n is an integer of 1 or more and 3 or less. and has one or more groups represented by the formula, at least one -Y Ｎ -Z Ｎ ｎ is a compound bonded to the nitrogen atom of the amine skeleton; wherein the polyol-modified product is a compound in which one or more hydroxy groups of a polyol are substituted with a group represented by the following formula: -Y Ｏ -Z Ｏ ｎ [In the formula, Y Ｏ is a (1 + n)-valent group composed of one or more selected from the group consisting of Y Ｏ１ and Y Ｏ２ and is composed of one or more selected from the group consisting of Y Ｏ１ is a group composed of one or more selected from the group consisting of 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, in each occurrence, independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms). Y Ｏ２ is a group composed of one or more selected from the group consisting of a divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a divalent to tetravalent hydrocarbon aromatic ring which may have a substituent, and a divalent to tetravalent heterocyclic ring which may have a substituent, Z Ｏ is a monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a monovalent polysiloxane group, n is an integer of 1 or more and 3 or less. and the polycarboxylic acid-modified product is a compound in which one or more carboxyl groups of a polycarboxylic acid are substituted with a hydroxy group of a group represented by the following formula: -Y Ｃ -Z Ｃ ｎ [In the formula, Y Ｃ is a (1 + n)-valent group composed of one or more selected from the group consisting of Y Ｃ１ and Y Ｃ２ and is composed of one or more selected from the group consisting of Y Ｃ１ is a group composed of one or more selected from the group consisting of direct bond, -O-, -C(=O)-, -C(=NR')-, -C(=S)-, -S-, -S(=O) ２ -, -NR'-, -C(OR')R'-, -C(OR')(-) ２ , and -N(-) ２ (wherein R' is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms). Y Ｃ２ is a group composed of one or more selected from the group consisting of a divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a divalent to tetravalent hydrocarbon aromatic ring which may have a substituent, and a divalent to tetravalent heterocyclic ring which may have a substituent, Z Ｃ is a monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a monovalent polysiloxane group, n is an integer of 1 or more and 3 or less. 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, wherein the polyol is glucose, fructose, galactose, xylose; sucrose, cycloamylose, cyclodextrin, maltose, trehalose, lactose, sucralose; sorbitol, maltitol, erythritol, isomalt, lactitol, mannitol, xylitol, sorbitan, lactitol; Starch, cellulose, curdlan, pullulan, alginic acid, carrageenan, guar gum, chitin, chitosan, locust bean gum, kappa-carrageenan, iota-carrageenan, isomalto-dextrin, gellan gum, tamarind seed gum; Cochinic acid, cinnamic acid, chlorogenic acid, gluconic acid; Glucosamine; Ascorbic acid, inositol; Catechin, quercetin, anthocyanin; Glycerin, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, trimethylolpropane, trimethylolethane; 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, wherein the polycarboxylic acid is Citric acid, malic acid, glutaric acid, adipic acid, phthalic acid, alginic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, aldic acid; Tricarballylic acid, t-aconitic acid, trimellitic acid; Pyromellitic acid; The following formula CH ２ =C(-Q)-C(=O)-OH [wherein, 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 oil-resistant agent composition according to claim 4, which is at least one selected from the group consisting of these and their derivatives.

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

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

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

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

10. The dispersant is 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, the oil-resistant agent composition according to claim 1.

11. The oil-resistant agent composition is in tablet form, and its particle size is 2000 to 100000 μm, the oil-resistant agent composition according to claim 1.

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

13. The oil-resistant agent composition according to claim 1 further comprises at least one selected from the group consisting of a lubricant, a binder, and a disintegrant.

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

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

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

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

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

19. Preparing an aqueous dispersion of an oil-resistant agent composition by mixing the oil-resistant agent composition according to any one of claims 1 to 14 with water, A method for producing a paper product, which comprises treating paper by external sizing or internal sizing using the aqueous dispersion.

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

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