Oil-resistant agent

Abstract

To provide a novel agent for imparting oil resistance, which is capable of imparting oil resistance to a base material, particularly a pulp base material.SOLUTION: The present invention provides an agent for imparting oil resistance comprising a liquid-repellent compound and a lignin compound.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This disclosure relates to repellents, particularly oil-resistant agents. [Background technology]

[0002] Patent Document 1 discloses an aqueous dispersion of an acrylamide polymer that can impart an excellent compressive strength improvement effect to cardboard. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2014-237795 [Overview of the project] [Problems that the invention aims to solve]

[0004] Patent Document 1 does not describe or suggest any application of imparting oil resistance to pulp substrates or as an oil-resistant agent.

[0005] The purpose of this disclosure is to provide a novel oil-resistant agent that can impart oil resistance to a substrate (particularly a pulp substrate). [Means for solving the problem]

[0006] This disclosure includes the following aspects: [Section 1] Oil-resistant agent containing liquid-repellent compounds and lignin compounds. [Section 2] The oil-resistant agent according to item 1, wherein the lignin compound has an ionic group other than a phenolic hydroxyl group. [Section 3] The oil-resistant agent according to claim 1 or 2, wherein the lignin compound is a lignin sulfonate. [Section 4] The oil-resistant agent according to any one of claims 1 to 3, wherein the lignin compound is sodium ligninsulfonate. [Section 5] The oil-resistant agent according to any one of claims 1 to 4, wherein the liquid-repellent compound is a compound having at least one selected from the group consisting of a hydrocarbon group having 6 or more carbon atoms which may have substituents, and a polysiloxane group. [Section 6] The oil-resistant agent according to claim 5, wherein the liquid-repellent compound is at least one selected from the group consisting of vinyl polymers, amine modifiers, polyol modifiers, polycarboxylic acid modifiers, isocyanate derivatives, waxes, and silicones. [Section 7] The oil-resistant agent according to claim 5 or 6, wherein the liquid-repellent compound is at least one selected from the group consisting of (meth)acrylic polymers, styrene polymers, polysiloxane group-containing (meth)acrylic polymers, hydrocarbon waxes, polyurethanes, silicone resins, fatty acid esters, fatty acid amides, and modified starches. [Section 8] The oil-resistant agent according to any one of claims 1 to 7, wherein the liquid-repellent compound is a (meth)acrylic polymer having a chain-like alkyl group with 12 to 18 carbon atoms. [Section 9] The oil-resistant agent according to any one of claims 1 to 8, wherein the hexadecane contact angle of the liquid-repellent compound is 25° or more. [Section 10] The oil resistant agent according to any one of claims 1 to 9, wherein the charge density of the oil resistant agent is -1500 μeq / g or more and 0 μeq / g or less. [Section 11] The liquid-repellent compound is a (meth)acrylic polymer having 50% by weight or more of repeating units derived from monomer (a1), The monomer (a1) Formula (a1): CH2=C(-X a1 )-C(=O)-Y a11 -Z(-Y a12 -R a1 ) n [In the formula, R a1 Each of these is independently a hydrocarbon group having 6 to 40 carbon atoms. X a1 is a hydrogen atom, a monovalent organic group, or a halogen atom. Y a11 is -O- or -NH-, Y a12 is, independently of each other, a group composed of at least one selected from a direct bond, or -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.] The oil-resistant agent according to claim 1 or 2, which is a monomer represented by [Item 12] An oil-resistant pulp product, in which the liquid-repellent compound and the lignin compound in the oil-resistant agent according to any one of Items 1 to 10 adhere to a pulp base material. [Item 13] The oil-resistant pulp product according to Item 11, wherein the amount of the liquid-repellent compound is 0.03% by weight or more and 3.0% by weight or less based on the pulp base material. [Item 14] The oil-resistant pulp product according to Item 12 or 13, which is a pulp molded product. [Item 15] The oil-resistant pulp product according to any one of Items 12 to 14, which is a food packaging material or a food container. [Item 16] A method for producing an oil-resistant pulp product, which includes a step of treating a pulp base material by external addition treatment or internal addition treatment with the oil-resistant agent according to any one of Items 1 to 11.

Advantages of the Invention

[0007] According to the present disclosure, oil resistance can be imparted to a base material (particularly a pulp base material).

Modes for Carrying Out the Invention

[0008] <Definition of Terms> As used herein, "n-valent group" means a group having n bonds, that is, a group that forms n bonds. Furthermore, "n-valent organic group" means an n-valent group containing carbon. Such organic groups are not particularly limited, but may be hydrocarbon groups or derivatives thereof. A hydrocarbon group derivative 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 a hydrocarbon group.

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

[0010] In this specification, unless otherwise stated, whether or not the phrases "independently in each occurrence," "independently of each other," "independently of each other," or similar expressions are explicitly stated, when a term (symbol) that may appear multiple times in a chemical structure is defined, the definition shall apply independently to each occurrence.

[0011] The chemical structures described herein should be understood to exclude any chemical structures that would be considered chemically impossible or extremely unstable by those skilled in the art.

[0012] <Oil repellent (oil-resistant agent)> The repellent agents in this disclosure adhere to a substrate (particularly 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 water-resistant agents, oil-resistant agents, water-repellent agents, oil-repellent agents, and / or antifouling agents. The repellent agents in this disclosure are particularly suitable as oil-resistant agents for imparting oil resistance to a substrate (particularly a pulp substrate).

[0013] Since the adhesion of chemicals to the surface of a pulp substrate is a reversible reaction, it is thought that the adhesion will not be maintained when shear is applied. In particular, prolonged stirring continuously applies shear, which is thought to be detrimental to chemical fixation. Nevertheless, the inventors of this application have unexpectedly found that by using the repellent agent of this disclosure, even when the pulp slurry is stirred for a long time (e.g., 30 minutes or more) after the repellent agent is added, the resulting product (e.g., pulp mold) exhibits excellent high-temperature oil resistance.

[0014] The repellent agent of this disclosure contains a liquid-repellent compound as described below as an active ingredient. The liquid-repellent compound itself may be used as a repellent agent, or it may be used as a repellent agent in combination with other components. Furthermore, it is preferable that the repellent agent of this disclosure contains a lignin compound as described below. By including a lignin compound, the effects of this disclosure can be well achieved.

[0015] The repellent agent in this disclosure does not necessarily have to contain any compound selected from the group consisting of a compound having 8 or more carbon atoms in a fluoroalkyl group, a compound having 8 or more carbon atoms in a perfluoroalkyl group, a compound having 4 or more carbon atoms in a fluoroalkyl group, a compound having 4 or more carbon atoms in a perfluoroalkyl group, a compound having a perfluoroalkyl group, a compound having a fluoroalkyl group, and a compound having a fluorine atom. The repellent agent in this disclosure can impart liquid repellency to a substrate even without containing these fluorine compounds.

[0016] The volume abundance of particles 100 μm or larger, as measured by laser diffraction scattering in the repellent of this disclosure, 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, and may also be 50% or less, 30% or less, 20% or less, 15% or less, 10% or less, 5% or less, 3% or less, or 1.5% or less, preferably 20% or less, and more preferably 5% or less. The method for achieving such a volume abundance of particles within the above range is not limited, but for example, the particles in the raw material and / or dispersion can be finely ground using a pulverizer or homogenizer.

[0017] The volume abundance of particles 10 μm or larger, as measured by laser diffraction scattering in the compositions of this disclosure, 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, and may also be 50% or less, 30% or less, 20% or less, 15% or less, 10% or less, 5% or less, 3% or less, or 1.5% or less, preferably 30% or less, more preferably 15% or less. The method for achieving such a volume abundance of particles within the above range is not limited, but for example, the particles in the raw material and / or dispersion can be micronized using a pulverizer or homogenizer.

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

[0019] The average particle size obtained from scanning electron microscope images of particles obtained by removing the liquid medium from a water-dispersible composition of a repellent agent (e.g., an oil-resistant agent for pulp) of the present disclosure by natural drying at room temperature may be 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.2 μm or more, 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, or 0.6 μm or more, and may also be 10 μm or less, 5 μm or less, 3 μm or less, 1 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, 0.3 μm or less, or 0.2 μm or less, preferably 1 μm or less. To achieve a particle size within the above range, for example, the particles in the raw material and / or dispersion can be finely ground using a pulverizer or homogenizer. Room temperature is defined as 20°C to 30°C, and especially 25°C.

[0020] The ionic charge density in the repellent of this disclosure may be -1000 μeq / g or more, -800 μeq / g or more, -600 μeq / g or more, -500 μeq / g or more, -400 μeq / g or more, -250 μeq / g or more, -100 μeq / g or more, -50 μeq / g or more, -25 μeq / g or more, 0 μeq / g or more, 1 μeq / g or more, 25 μeq / g or more, 50 μeq / g or more, 100 μeq / g or more, or 200 μeq / g or more, preferably -600 μeq / g or more, for example, -400 μeq / g or more, -200 μeq / g or more, or -50 μeq / g or more, and also 5000 μeq / g or less. The amount may be 2500 μeq / g or less, 1000 μeq / g or less, 750 μeq / g or less, 600 μeq / g or less, 500 μeq / g or less, 400 μeq / g or less, 350 μeq / g or less, 300 μeq / g or less, 200 μeq / g or less, 100 μeq / g or less, or 50 μeq / g or less, preferably 1000 μeq / g or less, more preferably 500 μeq / g or less, for example 300 μeq / g or less, particularly 100 μeq / g or less, and in a preferred embodiment, it may be -1500 μeq / g or more and 1500 μeq / g or less, particularly -1500 μeq / g or more and 0 μeq / g or less.

[0021] The anion demand of a sample solution containing 0.1 g / L solids is measured using a particle charge meter (BTG MUTEK PCD-06) with a 1 / 1000 N potassium polyvinylsulfonate solution, and the ion charge density (cation charge density) is calculated from the following formula (1). Alternatively, the cation demand is measured similarly using a polydiallyldimethylammonium chloride solution instead of potassium polyvinylsulfonate, and the ion charge density (anion charge density) is calculated from the following formula (1). Ion charge density (μeq / g) = A / B (1) A: Cation demand or anion demand (μeq / L) B: Sample solution concentration (g / L)

[0022] [Lignin compounds] The repellent agent in this disclosure comprises a lignin compound. By including a lignin compound, the effects of this disclosure can be effectively achieved. For example, by including a lignin compound, the stability of the repellent agent when it is in an aqueous dispersion can be improved.

[0023] In this disclosure, the lignin compound is a compound selected from lignin and modified lignin. Modified lignin is a compound whose main component is a structure derived from lignin, in which a part of the lignin is chemically modified and / or reduced in molecular weight, and may be a derivative of lignin, a decomposition product of lignin, a derivative of a decomposition product of lignin, etc. Specific examples of lignin compounds include, for example, lignin, ligninsulfonic acid, Kraft lignin, soda lignin, soda-anthraquinone lignin, organosol lignin, explosion lignin, lignin sulfate, etc. Of these, ligninsulfonic acid and Kraft lignin are preferred.

[0024] The lignin compound has phenolic hydroxyl groups, and the amount of phenolic hydroxyl groups may be 1.5% or more, preferably 1.6% or more, more preferably 1.7% or more, and may also be 20% or less, 15% or less, 10% or less, or 6.0% or less, preferably 5.5% or less, more preferably 5.0% or less, and in one embodiment it is 1.5-6.0%, 1.6-5.5%, or 1.7-5.0%. Furthermore, if the lignin compound is kraft lignin, the amount of phenolic hydroxyl groups is more preferably 2.0% or more, and particularly preferably more than 2.5%.

[0025] The amount of phenolic hydroxyl groups can be measured by measuring the differential extinction coefficient around 300 nm using a spectrophotometer. For example, by subtracting the absorption spectrum of a neutral solution containing the same concentration of lignin from the absorption spectrum of an alkaline solution containing a lignin sample (lignin compound), an ionization difference spectrum can be obtained, and the following formula can be used: Phenolic hydroxyl group content (%) = 17 × Δαmax / 4100 × 100 The percentage of phenolic hydroxyl groups is determined from this. Δαmax [L / (g·cm)] represents the differential extinction coefficient. For details, please refer to Junzo Nakano (ed.), "The Chemistry of Lignin - Fundamentals and Applications - Revised and Enlarged Edition," Uni Publishing, published May 25, 1990, p. 541.

[0026] The weight-average molecular weight of the lignin compound may be 500 or more, 1,000 or more, 2,000 or more, 3,000 or more, or 5,000 or more, preferably 1,000 or more, and may also be 500,000 or less, 300,000 or less, 100,000 or less, 50,000 or less, or 30,000 or less, preferably 50,000 or less. The weight-average molecular weight may also be the polyethylene glycol equivalent molecular weight measured by GPC.

[0027] Lignin compounds may have functional groups other than phenolic hydroxyl groups (especially ionic groups), and examples of such functional groups include hydroxyl groups, carboxyl groups, polyalkylene oxide chains, sulfone groups, nitroxyl groups, carbonyl groups, phosphate groups, amino groups, epoxy groups, methylol groups, cyanate groups, isocyanate groups, vinyl groups, maleimide groups, etc., and ionic groups are particularly preferred, and anionic groups are preferred. This can further improve dispersibility. Examples of such functional groups include carboxyl groups, sulfone groups, and phosphate groups. Among these, sulfone groups are more preferred.

[0028] Lignin compounds possess phenolic hydroxyl groups and may also have ionic groups, and therefore function as ionic dispersants (ionic surfactants), particularly anionic dispersants (anionic surfactants).

[0029] The lignin compound preferably has sulfur-containing functional groups such as sulfo groups and thiols, and the sulfur content may be 0.1% by mass or more, 0.3% by mass or more, 0.5% by mass or more, and may also be 6% by mass or less, 5% by mass or less, 4% by mass or less, or 3% by mass or less.

[0030] Functional groups in lignin compounds can be measured quantitatively or qualitatively by instrumental analysis such as NMR, IR, and elemental analysis.

[0031] The lignin compound may contain constituent units derived from other compounds, to the extent that it does not impair the effects of the present disclosure. Examples of other compounds include (alkyl)phenols such as phenol and cresol; aromatic hydrocarbon compounds such as benzene and naphthalene.

[0032] Furthermore, it is difficult to uniformly determine the chemical structure of lignin compounds using general formulas or similar methods. This is because the molecular framework that constitutes lignin compounds has an extremely complex structure.

[0033] Lignin compounds may also be salts. Examples of salts include alkali metal salts such as sodium or potassium salts; alkaline earth metal salts such as calcium salts; ammonium salts; and salts of organic amines.

[0034] [Lignin sulfonic acid] The lignin compound is preferably a lignin sulfonic acid. A lignin sulfonic acid is a lignin compound modified with a sulfo group, and may be, for example, a compound having a skeleton in which a sulfo group is introduced by cleaving the carbon at the α-position of the side chain of the hydroxyphenylpropane structure of lignin.

[0035] Lignosulfonic acid may be a ligninsulfonate salt. Examples of salts include alkali metal salts such as sodium or potassium salts; alkaline earth metal salts such as calcium salts; ammonium salts; and salts of organic amines, for example, sodium ligninsulfonate.

[0036] Commercially available lignin sulfonic acid products may be used, such as Vanirex HW (manufactured by Nippon Paper Industries), Sun Extract M (manufactured by Nippon Paper Industries), Pearllex NP (manufactured by Nippon Paper Industries), Sunflow RH (manufactured by Nippon Paper Industries), POLYFON, and REAX (all manufactured by Ingevity). Commercially available sodium lignin sulfonate products may be used, for example, Sun Extract® P252 and Vanillex® N manufactured by Nippon Paper Industries, and Polyfon® F, Polyfon® T, Polyfon® O, and Polyfon® H manufactured by Ingevity Corporation.

[0037] The amount of lignin compound may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, per 100 parts by weight of the liquid-repellent compound, or 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less.

[0038] [Liquid repellent compound] The repellents in this disclosure include liquid-repellent compounds. The liquid-repellent compounds in this disclosure adhere to a substrate (particularly a pulp substrate) and impart to the substrate liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or antifouling properties, particularly oil resistance.

[0039] [Characteristics, etc.] The properties that liquid-repellent compounds may possess are shown below.

[0040] The HD (n-hexadecane) contact angle of the liquid-repellent compound may be 10° or more, 20° or more, 25° or more, 30° or more, 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 60° or more, or 65° or more, preferably 25° or more, more preferably 30° or more, and may also be 100° or less, 90° or less, or 75° or less. By having an HD contact angle of the liquid-repellent compound above the lower limit, good liquid repellency (especially oil repellency) can be imparted to the substrate. The HD contact angle is the static contact angle of the liquid-repellent compound with respect to the spin-coated film, and is obtained by dropping 2 μL of HD onto the spin-coated film at room temperature (25°C) and measuring the contact angle 1 second after dropping.

[0041] The water contact angle of the liquid-repellent compound is 35° or higher, 40° or higher, 45° or higher, 50° or higher, 55° or higher, 65° or higher, 75° or higher, 85° or higher, 90° or higher, or 100° or higher, and may also be 160° or lower, 140° or lower, 130° or lower, 120° or lower, 110° or lower, 100° or lower, or 90° or lower. By having a water contact angle of the liquid-repellent compound above the lower limit, good liquid repellency (especially water repellency) can be imparted to the substrate. The water contact angle is 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 at room temperature (25°C) and measuring the contact angle 1 second after the drop.

[0042] The liquid-repellent compound is preferably a bio-based compound having carbon of bio-derived origin. The degree of bio-basedness is measured in accordance with ASTM D6866. The degree of bio-basedness may be 20% or more, preferably 30% or more, more preferably 50% or more, even more preferably 60% or more, even more preferably 70% or more, and most preferably 80% or more or 90% or more, for example 100%. A high degree of bio-basedness means that the amount of fossil resource-based materials, such as petroleum, used is small, and from this viewpoint, a higher degree of bio-basedness of the liquid-repellent compound is preferable.

[0043] The biodegradability of the liquid-repellent compound after 180 days is preferably 5% or more. Higher biodegradability is preferable as it reduces the environmental impact. The biodegradability of the liquid-repellent compound after 180 days may be, for example, 10% or more, 20% or more, 30% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, preferably 30% or more, more preferably 50% or more, even more preferably 70% or more, and most preferably 80% or more. The biodegradability of the liquid-repellent compound after 60 days is preferably 5% or more. Higher biodegradability is preferable as it reduces the environmental impact. The biodegradability of the liquid-repellent compound after 60 days may be, for example, 10% or more, 15% or more, 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, or 45% or more, preferably 10% or more, and more preferably 30% or more. Such biodegradability may be as defined in JIS K 6953-1 or ASTM D6400.

[0044] 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, preferably 40°C or higher, and may also 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.

[0045] [Structure etc.] The liquid-repellent compounds in this disclosure do not necessarily have to contain any of the group selected from the group consisting of fluoroalkyl groups having 8 or more carbon atoms, perfluoroalkyl groups having 8 or more carbon atoms, fluoroalkyl groups having 4 or more carbon atoms, perfluoroalkyl groups having 4 or more carbon atoms, perfluoroalkyl groups, fluoroalkyl groups, and fluorine atoms. Even if the liquid-repellent compounds do not contain these fluorine-containing groups, they can still impart liquid repellency to the substrate.

[0046] The liquid-repellent compounds in this disclosure do not necessarily have to be fatty acid esters having glycosidic bonds. Fatty acid esters having glycosidic bonds are typically compounds in which a fatty acid is added via an ester bond to the hydroxyl group of a compound having a glycosidic bond (typically sugars (monosaccharides or polysaccharides)).

[0047] The liquid-repellent compound may be a compound having at least one group selected from the group consisting of a hydrocarbon group having 6 or more carbon atoms, which may have substituents, and a polysiloxane group. In particular, the liquid-repellent compound may be a compound having at least one group selected from the group consisting of a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have substituents, and a monovalent polysiloxane group.

[0048] (Carbonate groups with 6 or more carbon atoms that may have substituents) The liquid-repellent compound may have a hydrocarbon group having 6 or more carbon atoms, which may have substituents.

[0049] The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, particularly an aliphatic hydrocarbon group, such as a saturated or unsaturated aliphatic hydrocarbon group (alkyl group, alkenyl group, etc.). The hydrocarbon group may be branched, cyclic, or linear, and is more preferably linear.

[0050] Hydrocarbon groups are typically monovalent and may be located at the end of the molecule, and may have one or more methyl groups at the end of the hydrocarbon group. In this specification, hydrocarbon compounds (e.g., hydrocarbon waxes) are understood to consist only of a monovalent hydrocarbon group and one hydrogen atom, and for example, a C20 n-alkane (eicosane) is understood to consist only of a C20 alkyl group and one hydrogen atom.

[0051] The number of carbon atoms in the hydrocarbon group may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, preferably 6 or more, 10 or more, 12 or more, or 16 or more, and may also be 75 or less, 65 or less, 60 or less, 50 or less, 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 40 or less, 30 or less, 25 or less, or 20 or less, and in one embodiment, it may be 6 to 60, 6 to 40, 12 to 30, or 12 to 20. The number of carbon atoms in the hydrocarbon group is typically 6 to 40, but may be greater than 40, for example, if the liquid-repellent compound is a hydrocarbon compound (hydrocarbon wax).

[0052] The hydrocarbon group may have substituents, but it is preferable that it be unsubstituted. Examples of substituents include -OR', -N(R')2, -COOR', and halogen atoms (wherein 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 in each occurrence). The substituents may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In a hydrocarbon group 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, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less. For example, a hydrocarbon group may have 1 to 3 (e.g., 1) -OR' (especially -OH) substituents (e.g., not at the terminal ends).

[0053] (Polysiloxane group) The liquid-repellent compound may have a polysiloxane group. Similar to hydrocarbon groups having 6 or more carbon atoms, which may have substituents, the polysiloxane group can impart liquid repellency to the substrate.

[0054] A polysiloxane group is a group having a polysiloxane structure. In this specification, when the term "polysiloxane" is used, unless otherwise specified, it refers to an organopolysiloxane modified with an organic group.

[0055] The silicon number of the polysiloxane group may be 3 or more, 5 or more, 6 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, and may also be 50000 or less, 25000 or less, 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, for example, 500 or less.

[0056] The polysiloxane group may be monovalent and located at the end of the molecule, or it may be divalent or polyvalent and located inside the molecule, but it is preferably monovalent.

[0057] The polysiloxane group is represented by the following formula: -[-Si(R s )2-O-] a - [In the formula, R s In each instance, it is independently a hydrocarbon group or reactive group having 1 to 40 carbon atoms. 'a' is an integer between 5 and 10000 (inclusive). It may also be represented as follows.

[0058] R s This refers to a hydrocarbon group having 1 to 40 carbon atoms, or a reactive group.

[0059] 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.

[0060] Examples of hydrocarbon groups having 1 to 5 carbon atoms include methyl, ethyl, propyl, butyl, and pentyl groups (especially aliphatic hydrocarbon groups, especially alkyl groups, such as methyl or ethyl groups, especially methyl groups).

[0061] The hydrocarbon group having 6 to 40 carbon atoms may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, preferably an aliphatic hydrocarbon group, and particularly preferably a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be cyclic, linear, or branched, preferably linear. The number of carbon atoms in the hydrocarbon group may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, preferably 10 or more, more preferably 12 or more, and may also 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.

[0062] Examples of reactive groups are groups having a functional group (e.g., hydroxyl 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 a silicon atom or to an organic group directly bonded to a 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 alkylene groups with 2 to 10 carbon atoms are preferred. Divalent aromatic groups with 6 to 12 carbon atoms are preferred. The reactive group may be a group selected from the group consisting of hydroxyl group, epoxy ring, carboxyl group, (meth)acrylic group, and amino group, for example, at least one selected from the group consisting of epoxy ring, hydroxyl group, (meth)acrylic group, and carboxyl group.

[0063] a may be 3 or more, 5 or more, 6 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, and may also 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.

[0064] R is a hydrocarbon group with 1 to 5 carbon atoms in the polysiloxane group. s The amount is R s The amount of the total may be 20 mol% or more, 40 mol% or more, 60 mol% or more, or 80 mol% or more, preferably 50 mol% or more, and may also be 100 mol% or less, 90 mol% or less, 80 mol% or less, or 70 mol% or less. For example, R s It is also possible that 50 mol% or more of the total number of groups are methyl groups or ethyl groups (especially methyl groups).

[0065] R is a hydrocarbon group with 6 to 40 carbon atoms in the polysiloxane group. s The amount is R s The amount of the total may be 3 mol% or more, 10 mol% or more, 20 mol% or more, or 30 mol% or more, and may also be 100 mol% or less, 90 mol% or less, 80 mol% or less, or 70 mol% or less.

[0066] In the polysiloxane group, the reactive group R s The amount is R s The total amount may be 5 mol% or more, 10 mol% or more, 20 mol% or more, or 30 mol% or more, and may also be 50 mol% or less, 40 mol% or less, 30 mol% or less, or 20 mol% or less. The polysiloxane group is a reactive group R s It does not have to be included.

[0067] R s The elements may be introduced randomly or in blocks, but random is preferred.

[0068] The terminal structure of the polysiloxane group described above is not limited to -R s , -OR s , -Si(R s ) may be third class. R of terminal structure sIt may or may not have one or more reactive groups. Examples of reactive groups are as described above, and may be at least one selected from the group consisting of epoxy rings, hydroxyl groups, (meth)acrylic groups, and carboxyl groups.

[0069] The polysiloxane group may have a linker, and the parent structure and the polysiloxane group may be bonded via the linker. Such a linker is not limited to but may be a hydrocarbon group having 1 to 40 (e.g., 1 to 20) carbon atoms that may be interrupted by an oxygen atom, for example, a (poly)oxyalkylene group having 1 to 40 (e.g., 1 to 20) carbon atoms.

[0070] Examples of polysiloxane groups include: -[-Si(R s )2-O-] a -Si(R s )3 -L s1 -[-Si(R s )2-O-] a -Si(R s )3 -L s1 -OL s1 -[-Si(R s )2-O-] a -R s -L s1 -[-Si(R s )2-O-] a -Si(R s )3 -L s1 -OL s1 -[-Si(R s )2-O-] a -R s -L s1 -[-Si(R s )2-O-] a -Si(R s ) 3、 -L s1 -[-Si(R s )2-O-] a -R s [In the formula, R s In each instance, it is independently a hydrocarbon group or reactive group having 1 to 40 carbon atoms. R s More than 50 mol% of the total number of groups are methyl groups. L s1 In each instance, it is independently a hydrocarbon group having 1 to 20 carbon atoms. a is between 5 and 10000. TIFF0007832566000001.tif2169[In the formula, a represents an integer between 0 and 150, b represents an integer between 1 and 150, (a+b) is between 5 and 200, and n is an integer between 0 and 36.] These are some examples.

[0071] The polysiloxane group may have a silsesquioxane structure or a silica structure, thereby forming a branched structure (silicone resin structure), for example, -O-Si(R s )(-O-)2 -O-Si(-O-)3 A branched structure may be formed by such a branched structure.

[0072] [Examples of liquid-repellent compounds] The liquid-repellent compound may be at least one selected from the group consisting of vinyl polymers, amine modifiers, polyol modifiers, polycarboxylic acid modifiers, isocyanate derivatives, waxes, and silicones. For example, it may be at least one selected from the group consisting of (meth)acrylic polymers, styrene polymers, polysiloxane group-containing (meth)acrylic polymers, hydrocarbon waxes, polyurethanes, silicone resins, fatty acid esters, fatty acid amides, and modified starches. These liquid-repellent compounds preferably have at least one selected from the group consisting of a hydrocarbon group having 6 or more carbon atoms, which may have substituents, and a polysiloxane group. Details of the liquid-repellent compounds are described below.

[0073] The liquid-repellent compounds are -O(C=O)R, -COOR, -NHCOR, and -CONHR [In the formula, R is independently a hydrocarbon group or polysiloxane group having 6 to 40 carbon atoms, which may have substituents.] It may be a compound having at least one group selected from the group consisting of the following:

[0074] The liquid-repellent compound may contain an ester group, amide group, urethane group, urea group, imide group, thioamide group, thiourethane group, thiourea group, thioimide group, sulfonamide group, sulfonurea group, sulfonurethane group, or sulfonimide group (for example, an ester group, amide group, urethane group, urea group, or imide group). For example, the liquid-repellent compound may contain -C(=O)-O-, -OC(=O)-, -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'-, or -SO2NR'- (wherein R' is 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)). The liquid-repellent compound may also be a compound formed by bonding a modifying group (particularly a monovalent hydrocarbon group which may have the above substituents) to the starting material compound via at least one of these groups. The liquid-repellent compound may contain an amide structure. The liquid-repellent properties of the liquid-repellent compound can be improved by containing at least an amide structure. Here, the amide structure may be an amide structure in a broad sense, and may be selected from amide (acid amide) groups (or carboxylic acid amides), urethane groups, urea groups, imide groups, thioamide groups, thiourethane groups, thiourea groups, thioimide groups, sulfonamide groups, sulfonurethane groups, sulfonurea 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 (where each group may be oriented in a left-right inverted direction). Here, at least one of the bonds of the N in the amide structure may be bonded to a hydrogen atom. The amide structure is preferably -(C=O)N(-)2, and may be an amide structure of a group selected from the group consisting of amide groups, urethane groups, urea groups, and imide groups.

[0075] [Amount of liquid-repellent compound] The amount of the liquid-repellent compound may be 0.01% or more by weight, 0.03% or more by weight, 0.5% or more by weight, 1% or more by weight, 3% or more by weight, 5% or more by weight, 10% or more by weight, 20% or more by weight, or 30% or more by weight, and may also be 60% or less by weight, 50% or less by weight, 40% or less by weight, 30% or less by weight, 20% or less by weight, 10% or less by weight, 5% or less by weight, or 3% or less by weight. The liquid-repellent compound itself may also be used as the repellent.

[0076] [Vinyl polymer] As an example of a liquid-repellent compound, vinyl polymers will be described. Vinyl polymers are polymers formed by polymerizing vinyl monomers and exhibit liquid-repellent properties. Here, the vinyl monomer can be any compound having a polymerizable carbon-carbon double bond (ethylenically unsaturated double bond) (>C=C<), and may be a monomer containing a vinyl group, vinylene group, vinylidene group, acryloyl group, methacryloyl group, or derivative groups thereof.

[0077] [Characteristics, etc.] The vinyl polymer is preferably a compound having bio-based carbon. The degree of biobase is measured in accordance with ASTM D6866. The degree of biobase of the vinyl polymer may be 20% or more, preferably 30% or more, more preferably 50% or more, even more preferably 60% or more, even more preferably 70% or more, and most preferably 80% or more or 90% or more, for example 100%. A high degree of biobase means that the amount of fossil resource-based materials, such as petroleum, used is small, and from this viewpoint, a higher degree of biobase of the vinyl polymer is preferable.

[0078] 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, and may also 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.

[0079] [Structure etc.] The weight-average molecular weight of the vinyl polymer may be 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more, and may also be 5000000 or less, 3000000 or less, 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, or 5000 or less. The weight-average molecular weight may be the polystyrene-equivalent molecular weight measured by GPC.

[0080] (a) hydrocarbon group-containing monomers The vinyl polymer may have repeating units derived from a hydrocarbon group-containing monomer (a). Monomer (a) has one ethylenically unsaturated double bond and a hydrocarbon group having 6 to 40 carbon atoms.

[0081] The monomer (a) preferably has a (meth)acrylic group as the group having an ethylenically unsaturated double bond, for example, it may have a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond.

[0082] Monomer (a) has a hydrocarbon group having 6 to 40 carbon atoms. Referring to the above explanation of (hydrocarbon groups having 6 or more carbon atoms that may have substituents), it is preferable that the hydrocarbon group is unsubstituted. Here, the hydrocarbon group is a monovalent group. 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, and more preferably linear. The hydrocarbon group may be saturated or unsaturated. The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group (alkyl group). The number of carbon atoms in the hydrocarbon group may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, preferably 10 or more, 12 or more, 14 or more, or 16 or more, and may also 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.

[0083] 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 Each of these is 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 This is a group composed of at least one of the following: divalent to tetravalent carbon-1 hydrocarbon groups (especially -CH2-, -CH(-)2), -C6H4-, -O-, -C(=O)-, -S(=O)2-, or -NH-. k is between 1 and 3. It is preferable that the monomer is represented by .

[0084] X aThis may be a hydrogen atom, a methyl group, a halogen other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. a Examples include hydrogen atoms, methyl groups, chlorine atoms, bromine atoms, iodine atoms, and cyano groups. a It is preferable that the element is a hydrogen atom, a methyl group, or a chlorine atom. a It is particularly preferable that it be a hydrogen atom.

[0085] Y a It is a divalent to tetravalent group. a It is preferable that the group is divalent. Y a It is preferable that the group is composed of at least one of the following: a hydrocarbon group having 1 carbon atom, -C6H4-, -O-, -C(=O)-, -S(=O)2-, or -NH-. a It is preferable that it is not a hydrocarbon group. Examples of a C1 hydrocarbon group include -CH2-, -CH(-)2, or -C(-)3. A hydrocarbon group having C1 is repeated, and -(CH2) m -(m is an integer from 1 to 5) may form a hydrocarbon group with 2 or more carbon atoms. a It may have an NH group.

[0086] Y a -Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-R'-, -Y'-R'-Y'- , -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O)-Y'-, -Y'-R'-Y'-C(=O)-Y'-, or -Y'-R'-Y'-R'- [In the formula, Y' is a direct bond, -O-, -NH-, or -S(=O)2-, R' is -(CH2) m -(m is an integer between 1 and 5) or -C6H4- (phenylene group). That's fine.

[0087] Y aSpecific examples thereof 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 1 to 5, particularly 2 or 4].

[0088] Y a is -O-, -NH-, -O-(CH2) m-OC(=O)-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -OC(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -NH-S(=O)2-, -O-(CH2) m -S(=O)2-NH-, -NH-(CH2) m -NH-S(=O)2-, or -NH-(CH2) m -S(=O)2-NH- [In the formula, m is an integer between 1 and 5, in particular 2 or 4.] It is preferable that this is the case. a is -O- or -O-(CH2) m -NH-C(=O)-, especially -O-(CH2) m -NH-C(=O)- is more preferable.

[0089] R a Each of these is independently a hydrocarbon group having 6 to 40 carbon atoms, and, referring to the above explanation of (hydrocarbon groups having 6 or more carbon atoms that may have substituents), it is preferable that they are linear or branched hydrocarbon groups. The hydrocarbon group may be a linear hydrocarbon group in particular. The hydrocarbon group is preferably an aliphatic hydrocarbon group, especially a saturated aliphatic hydrocarbon group, and especially an alkyl group. The number of carbon atoms in the hydrocarbon group is preferably 12 to 30, for example, 12 to 18, 16 to 26, or 15 to 26, and especially 18 to 22 or 17 to 22.

[0090] A concrete example of monomer (a) is: Formula (a1): CH2=C(-X a1 )-C(=O)-Y a11 -Z(-Y a12 -R a1 ) n [In the formula, R a1 Each of these is independently a hydrocarbon group having 6 to 40 carbon atoms. X a1is a hydrogen atom, a monovalent organic group, or a halogen atom. Y a11 It is -O- or -NH-, Y a12 Each of these groups is independently composed of a direct bond or at least one selected from -O-, -C(=O)-, -S(=O)2-, -NH-, or -CH2-. Z is a directly bonded or divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms. n is either 1 or 2. A monomer represented by, and Formula (a2): CH2=C(-X a2 )-C(=O)-Y a2 -R a2 [In the formula, R a2 This is a hydrocarbon group having 6 to 40 carbon atoms. X a2 is a hydrogen atom, a monovalent organic group, or a halogen atom. Y a2 It is -O- or -NH-. monomer represented by That is the case.

[0091] (a1) monomer Monomer (a1) is a different monomer from monomer (a2).

[0092] Monomer (a1) may be a monomer having a hydrocarbon group with 6 to 40 carbon atoms and an NH group-containing group. Monomer (a1) may contain an amide group, a urea group, a urethane group, or a sulfonamide group. The NH group-containing group may be an amide group, a urea group, a urethane group, or a sulfonamide group. The hydrocarbon monomer may be a combination of a hydrocarbon monomer having an amide group, a urea group, a urethane group, or a sulfonamide group and a hydrocarbon monomer not having an amide group, a urea group, a urethane group, or a sulfonamide group. The effects of this disclosure can be well achieved by including such groups in monomer (a1).

[0093] Monomer (a1) 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-.

[0094] The monomer (a1) is given by formula: CH2=C(-X a1 )-C(=O)-Y a11 -Z(-Y a12 -R a1 ) n [In the formula, R a1 Each of these is independently a hydrocarbon group having 6 to 40 carbon atoms. X a1 is a hydrogen atom, a monovalent organic group, or a halogen atom. Y a11 It is -O- or -NH-, Y a12 Each of these groups is independently composed of a direct bond or at least one selected from -O-, -C(=O)-, -S(=O)2-, -NH-, or -CH2-. Z is a directly bonded or divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms. n is either 1 or 2. It may be a compound represented by Y. a12 And / or Z does not have to be directly connected. a12 And Z do not necessarily have to be directly bonded at the same time.

[0095] R a1 It is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, and especially an alkyl group. a1 In this, the number of carbon atoms in the hydrocarbon group is preferably 12 to 30, for example 16 to 26 or 15 to 26, and particularly preferably 18 to 22 or 17 to 22.

[0096] X a1 This may be a hydrogen atom, a methyl group, a halogen other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. A hydrogen atom, a methyl group, or a chlorine atom is preferred.

[0097] Y a12 -Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-R'-, -Y'-R'-Y'- , -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O)-Y'-, -Y'-R'-Y'-C(=O)-Y'-, or -Y'-R'-Y'-R'- [In the formula, Y' is independently a direct bond, -O-, -NH-, or -S(=O)2-, R' is -(CH2) m -(m is an integer from 1 to 5), a linear hydrocarbon group having an unsaturated bond with 1 to 5 carbon atoms, a branched hydrocarbon group having 1 to 5 carbon atoms, or -(CH2) l -C6H4-(CH2) l -(where l is an independent integer between 0 and 5, and -C6H4- is a phenylene group). That's fine.

[0098] Y a12 Specific examples include direct bond, -O-, -NH-, -OC(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S(=O)2-, -S (=O)2-NH-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C6H4-, -NH-C6H4-, -O-(CH2) m -O-, -NH-(CH2) m -NH-, -O-(CH2) m -NH-, -NH-(CH2) m -O-, -O-(CH2) m -OC(=O)-, -O-(CH2) m -C(=O)-O-, -NH-(CH2) m -OC(=O)-, -NH-(CH2) m -C(=O)-O-, -O-(CH2) m -OC(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -C(=O)-NH-, -O-(CH2) m-NH-C(=O)-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -O-C6H4-, -NH-(CH2) m -OC(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -NH-C(=O)-NH-, -NH-(CH2) m -O-C6H4-, -NH-(CH2) m -NH-C6H4- [In the formula, m is an integer between 1 and 5.] That is the case.

[0099] Especially Y a12 It may have an NH group.

[0100] Y a12 is preferably -O-, -NH-, -OC(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S(=O)2-, -S(=O)2-NH-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C6H4-. Y a12 It is more preferable that -NH-C(=O)-, -C(=O)-NH-, -OC(=O)-NH-, -NH-C(=O)-O-, or -NH-C(=O)-NH-. a12 The bond does not have to be a direct one.

[0101] Z is a directly bonded, or divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and may have a linear or branched structure. The number of carbon atoms in Z is preferably 2 to 4, particularly 2. Specific examples of Z are directly bonded, -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH2CH(-)2, -CH2(CH-)CH2-, -CH2CH2CH(-)2, -CH2CH2(CH-)CH2-, and -CH2CH2CH2CH(-)2. Z does not have to be directly bonded.

[0102] The monomer (a1) is CH2=C(-X a1 )-C(=O)-O-(CH2) m -NH-C(=O)-R a1 CH2=C(-X a1 )-C(=O)-O-(CH2) m -OC(=O)-NH-R a1 CH2=C(-X a1 )-C(=O)-O-(CH2) m -NH-C(=O)-OR a1 CH2=C(-X a1 )-C(=O)-O-(CH2) m -NH-C(=O)-NH-R a1 It is preferable that R a1 and X a1 This is synonymous with the above. The monomer (a1) is CH2=C(-X a1 )-C(=O)-O-(CH2) m -NH-C(=O)-R a1 It is particularly preferable that this be the case.

[0103] Monomer (a1) can be produced by reacting a hydroxyalkyl (meth)acrylate or hydroxyalkyl (meth)acrylamide with a long-chain alkyl isocyanate. Examples of long-chain alkyl isocyanates include lauryl isocyanate, myristyl isocyanate, cetyl isocyanate, stearyl isocyanate, oleyl isocyanate, and behenyl isocyanate. Alternatively, monomer (a1) can be produced by reacting a (meth)acrylate having an isocyanate group in its side chain, such as 2-methacryloyloxyethyl methacrylate, with a long-chain alkylamine or long-chain alkyl alcohol. Examples of long-chain alkylamines include laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, and behenylamine. Examples of long-chain alkyl alcohols include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and behenyl alcohol.

[0104] A preferred example of monomer (a) is as follows: Stearyl (meth)acrylate, behenyl (meth)acrylate, stearyl α-chloroacrylate, behenyl α-chloroacrylate; Stearyl(meth)acrylamide, behenyl(meth)acrylamide;

[0105] TIFF0007832566000002.tif2453

[0106] TIFF0007832566000003.tif2253 TIFF0007832566000004.tif2152 TIFF0007832566000005.tif2155

[0107] TIFF0007832566000006.tif2357 TIFF0007832566000007.tif2256 TIFF0007832566000008.tif2156

[0108] TIFF0007832566000009.tif2051 TIFF0007832566000010.tif2054 TIFF0007832566000011.tif2352 TIFF0007832566000012.tif2659

[0109] TIFF0007832566000013.tif2046

[0110] TIFF0007832566000014.tif2249 [In the above formula, n is a number between 6 and 40, and m is a number between 1 and 5.] The compound with the above chemical formula is an acrylic compound in which the α-position is a hydrogen atom, but specific examples may include a methacle compound in which the α-position is a methyl group and an α-chloroacrylic compound in which the α-position is a chlorine atom.

[0111] The monomer (a1) is given by formula: R a12 -C(=O)-NH-R a13 -OR a11 [In the formula, R a11 This is an organic residue having an ethylenically unsaturated polymerizable group. R a12 This is a hydrocarbon group having 6 to 40 carbon atoms. R a13 This is a hydrocarbon group having 1 to 5 carbon atoms. It is preferable that the monomer is an amide group-containing monomer represented by [formula].

[0112] R a11 This is an organic residue having an ethylenically unsaturated polymerizable group, and is not particularly limited as long as it has a polymer carbon carbon-carbon double bond. Specifically, -C(=O)CR a111 =CH2, -CHR a111 =CH2, -CH2CHR a111Examples include organic residues having ethylenically unsaturated polymerizable groups such as CH2, and R a111 Examples include hydrogen atoms or alkyl groups having 1 to 4 carbon atoms. Also, R a11 In addition to ethylenically unsaturated polymerizable groups, it may have various organic groups, such as chain hydrocarbons, cyclic hydrocarbons, polyoxyalkylene groups, and polysiloxane groups, and these organic groups may be substituted with various substituents. a11 is -C(=O)CR a111 It is preferable that the formula is CH2.

[0113] R a12 The hydrocarbon group possessed by monomer (a) is as described above, and is a hydrocarbon group having 6 to 40 carbon atoms, preferably an alkyl group, and includes chain hydrocarbon groups, cyclic hydrocarbon groups, etc. Among these, it is preferably a chain hydrocarbon group, and particularly preferably a linear saturated hydrocarbon group. a12 The number of carbon atoms is 6 to 40, but preferably 11 to 27, and particularly preferably 15 to 23.

[0114] R a13 This 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 linear or branched, and may have unsaturated bonds, but linear is preferred. a13 The number of carbon atoms is preferably 2 to 4, and particularly preferably 2. a13 It is preferable that it is an alkylene group.

[0115] A monomer containing an amide group is R a12 Those that have only one type (for example, R a12 (Only compounds with 17 carbon atoms), or R a12 Those that are multiple combinations (for example, R a12 A compound with 17 carbon atoms and R a12 It may be a mixture of a compound having 15 carbon atoms.

[0116] An example of an amide group-containing monomer is carboxylic acid amide alkyl (meth)acrylate. Specific examples of amide group-containing monomers include palmitic acid amidoethyl (meth)acrylate, stearic acid amidoethyl (meth)acrylate, beheninic acid amidoethyl (meth)acrylate, myristateic acid amidoethyl (meth)acrylate, lauric acid amidoethyl (meth)acrylate, isostearate ethyl amide (meth)acrylate, oleic acid ethyl amide (meth)acrylate, tert-butylcyclohexylcaproic acid amidoethyl (meth)acrylate, adamantane carboxylic acid ethyl amide (meth)acrylate, naphthalene carboxylic acid amidoethyl (meth)acrylate, anthracene carboxylic acid amidoethyl (meth)acrylate, palmitic acid amidopropyl (meth)acrylate, stearic acid amidopropyl (meth)acrylate, palmitic acid amidoethyl vinyl ether, stearic acid amidoethyl vinyl ether, palmitic acid amidoethyl allyl ether, stearic acid amidoethyl allyl ether, or mixtures thereof.

[0117] The amide group-containing monomer is preferably stearamide ethyl (meth)acrylate. The amide group-containing monomer may be a mixture containing stearamide ethyl (meth)acrylate. In a mixture containing stearamide ethyl (meth)acrylate, the amount of stearamide ethyl (meth)acrylate may be, for example, 40% or more by weight, 50% or more by weight, 60% or more by weight, or 70% or more by weight, and may be 90% or less by weight, 80% or less by weight, or 70% or less by weight, based on the total weight of the amide group-containing monomer. The remaining monomer may be, for example, palmitate ethyl (meth)acrylate.

[0118] (a2) monomer The monomer (a2) is given by the formula: CH2=C(-X a2 )-C(=O)-Y a2 -R a2 [In the formula, R a2 This is a hydrocarbon group having 6 to 40 carbon atoms. X a2is a hydrogen atom, a monovalent organic group, or a halogen atom. Y a2 It is -O- or -NH-. It is a compound represented by [formula].

[0119] The monomer (a2) is Y a2 A long-chain acrylate ester monomer in which is -O-, or Y a2 It is a long-chain acrylamide monomer with -NH-. R a2 It is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, and especially an alkyl group. a2 In this case, the number of carbon atoms in the hydrocarbon group is preferably 12 to 30, for example 16 to 26, and particularly preferably 18 to 22. X a2 This may be a hydrogen atom, a methyl group, a halogen other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. A hydrogen atom, a methyl group, or a chlorine atom is preferred.

[0120] Preferred examples of long-chain acrylate ester monomers are lauryl (meth)acrylate, stearyl (meth)acrylate, icosyl (meth)acrylate, behenyl (meth)acrylate, stearyl α-chloroacrylate, icosyl α-chloroacrylate, and behenyl α-chloroacrylate. Preferred examples of long-chain acrylamide monomers are stearyl(meth)acrylamide, eicosyl(meth)acrylamide, and behenyl(meth)acrylamide.

[0121] (b) Hydrophilic group-containing monomer The vinyl polymer may contain repeating units derived from a hydrophilic group-containing monomer (b). Monomer (b) is a monomer other than monomer (a) that has a hydrophilic group.

[0122] Monomer (b) preferably has a (meth)acrylic group as the group having an ethylenically unsaturated double bond, for example, it may have a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond. Monomer (a) may have one or two groups having an ethylenically unsaturated double bond, but it is preferable to have only one.

[0123] The hydrophilic group is preferably an oxyalkylene-containing group (the alkylene group has 2 to 6 carbon atoms), and is particularly preferably an oxyethylene group. In particular, monomer (b) is preferably an oxyalkylene (meth)acrylate, such as polyalkylene (or monoalkylene) glycol mono(meth)acrylate and / or polyalkylene (or monoalkylene) glycol di(meth)acrylate, or polyalkylene (or monoalkylene) glycol mono(meth)acrylamide.

[0124] Monomer (b) is, formula: CH2=CX b C(=O)-Y b -(R b O) n -A b [In the formula, X b is a hydrogen atom or a methyl group, Y b It is -O- or -NH-, R b These are each an alkylene group having 2 to 6 carbon atoms, A b This is a hydrogen atom, an unsaturated or saturated hydrocarbon group with 1 to 22 carbon atoms, or CH2=CX b C(=O)- exists, n is an integer between 1 and 90. It is preferable that the oxyalkylene (meth)acrylate is represented by [formula].

[0125] An example of monomer (b) is given by formula: CH2=CX b C(=O)-O-(Rb O) n -A bi (b1) and CH2=CX b C(=O)-O-(R b O) n -C(=O)CX b =CH2(b2), CH2=CX b C(=O)-NH-(R b O) n -A bi (b3) [In the formula, X b Each of these is independently a hydrogen atom or a methyl group, R b These are each an alkylene group having 2 to 6 carbon atoms, A bi Each of these is independently a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms. n is an integer between 1 and 90. That is the case. Preferably, these are represented by monomers (b1), monomer (b2), and monomer (b3), respectively.

[0126] n can be, for example, 1 to 50, especially 1 to 30, or more specifically 1 to 15 or 2 to 15. Alternatively, n can be, for example, 1. R b This may be a linear or branched alkylene group, for example, formula -(CH2) x - or - (CH2) x1 -(CH(CH3)) x2 -[In the formula, x1 and x2 are between 0 and 6, for example, between 2 and 5, and the sum of x1 and x2 is between 1 and 6. -(CH2) x1 -and-(CH(CH3)) x2 The order of the hyphens is not limited to the given formula and may be random. The base may be represented by ]. -(R b O) n -In this case, R may be of two or more types (for example, 2 to 4 types, especially 2 types), -(R b O) n- is, for example, -(R 1 O) n1 -and-(R 2 O) n2 -[wherein, R 1 and R 2 The combination may be: 1, n1 and n2 are mutually distinct 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 between 2 and 90.

[0127] R in equations (b1), (b2), and (b3) b R is particularly preferably an ethylene group, a propylene group, or a butylene group, especially a butylene group. b R may be a combination of two or more alkylene groups. In that case, it is preferable that at least one of R is an ethylene group, a propylene group, or a butylene group. b Examples of combinations include ethylene group / propylene group combinations, ethylene group / butylene group combinations, and propylene group / butylene group combinations. Monomer (b) may be a mixture of two or more types. In that case, at least one of monomer (b) is R in formula (b1), (b2), or (b3). b It is preferable that the group is an ethylene group, a propylene group, or a butylene group. Furthermore, when using polyalkylene glycol di(meth)acrylate represented by formula (b2), it is not preferable to use it alone as monomer (b), but rather to use it in combination with monomer (b1). In that case as well, it is preferable that the compound represented by formula (b2) be kept to less than 30% by weight of the monomer (b) used.

[0128] Specific examples of monomer (b) include, but are not limited to, the following. CH2=CHCOO-CH2CH2O-H CH2=CHCOO-CH2CH2CH2O-H CH2=CHCOO-CH2CH(CH3)OH CH2=CHCOO-CH(CH3)CH2O-H CH2=CHCOO-CH2CH2CH2CH2O-H CH2=CHCOO-CH2CH2CH(CH3)OH CH2=CHCOO-CH2CH(CH3)CH2O-H CH2=CHCOO-CH(CH3)CH2CH2O-H CH2=CHCOO-CH2CH(CH2CH3)OH CH2=CHCOO-CH2C(CH3)2O-H CH2=CHCOO-CH(CH2CH3)CH2O-H CH2=CHCOO-C(CH3)2CH2O-H CH2=CHCOO-CH(CH3)CH(CH3)OH CH2=CHCOO-C(CH3)(CH2CH3)OH CH2=CHCOO-(CH2CH2O)2-H CH2=CHCOO-(CH2CH2O)4-H CH2=CHCOO-(CH2CH2O)5-H CH2=CHCOO-(CH2CH2O)6-H CH2=CHCOO-(CH2CH2O)5-CH3 CH2=CHCOO-(CH2CH2O)9-CH3 CH2=CHCOO-(CH2CH2O) 23 -CH3 CH2=CHCOO-(CH2CH2O) 90 -CH3

[0129] 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

[0130] 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

[0131] 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

[0132] 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)OH CH2=CH-C(=O)-NH-CH2C(CH3)2O-H CH2=CH-C(=O)-NH-CH(CH2CH3)CH2O-H CH2=CH-C(=O)-NH-C(CH3)2CH2O-H CH2=CH-C(=O)-NH-CH(CH3)CH(CH3)OH CH2=CH-C(=O)-NH-C(CH3)(CH2CH3)OH CH2=CH-C(=O)-NH-(CH2CH2O)2-H CH2=CH-C(=O)-NH-(CH2CH2O)4-H CH2=CH-C(=O)-NH-(CH2CH2O)5-H CH2=CH-C(=O)-NH-(CH2CH2O)6-H CH2=CH-C(=O)-NH-(CH2CH2O)9-H CH2=CH-C(=O)-NH-(CH2CH2O)5-CH3 CH2=CH-C(=O)-NH-(CH2CH2O)9-CH3 CH2=CH-C(=O)-NH-(CH2CH2O) 23 -CH3 CH2=CH-C(=O)-NH-(CH2CH2O) 90 -CH3

[0133] 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

[0134] CH2=C(CH3)-C(=O)-NH-CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH(CH3)OH CH2=C(CH3)-C(=O)-NH-CH(CH3)CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH2CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH2CH(CH3)OH CH2=C(CH3)-C(=O)-NH-CH2CH(CH3)CH2O-H CH2=C(CH3)-C(=O)-NH-CH(CH3)CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH(CH2CH3)OH CH2=C(CH3)-C(=O)-NH-CH2C(CH3)2O-H CH2=C(CH3)-C(=O)-NH-CH(CH2CH3)CH2O-H CH2=C(CH3)-C(=O)-NH-C(CH3)2CH2O-H CH2=C(CH3)-C(=O)-NH-CH(CH3)CH(CH3)OH CH2=C(CH3)-C(=O)-NH-C(CH3)(CH2CH3)OH CH2=C(CH3)-C(=O)-NH-(CH2CH2O)2-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)4-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)6-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)9-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O)9-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O) 23 -CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O) 90 -CH3

[0135] 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

[0136] As monomer (b), X 2 It is preferable that the monomer (b) is a hydrogen atom and is an acrylate or acrylamide. Monomer (b) is particularly preferably hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or hydroxyethyl acrylamide.

[0137] (c) Monomers containing ionic groups The vinyl polymer may contain repeating units derived from an ionic group-containing monomer (c). The monomer (c) is preferably a monomer containing one ethylenically unsaturated double bond and an ionic group (particularly an acrylic monomer). The ionic group is an anionic group and / or a cationic group, or a salt thereof.

[0138] The monomer (c) preferably has a (meth)acrylic group as the ethylenically unsaturated double bond, for example, it may have a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond.

[0139] Monomers having anionic groups include monomers having a carboxyl group, a sulfonic acid group, or a phosphate group. Specific examples of monomers having anionic groups include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, vinylsulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, (meth)acrylate phosphoric acid, vinylbenzenesulfonic acid, acrylamide tert-butylsulfonic acid, or salts thereof.

[0140] Examples of salts of anionic groups include alkali metal salts, alkaline earth metal salts, or ammonium salts, such as methylammonium salt, ethanolammonium salt, and triethanolammonium salt.

[0141] In monomers having a cationic group, examples of cationic groups are amino groups, preferably tertiary and quaternary amino groups. In tertiary amino groups, the two groups bonded to the nitrogen atom are preferably the same or different aliphatic group having 1 to 5 carbon atoms (especially alkyl groups), aromatic groups having 6 to 20 carbon atoms (aryl groups), or aromatic aliphatic groups having 7 to 25 carbon atoms (especially aralkyl groups, e.g., benzyl group (C6H5-CH2-)). In quaternary amino groups, the three groups bonded to the nitrogen atom are preferably the same or different aliphatic group having 1 to 5 carbon atoms (especially alkyl groups), aromatic groups having 6 to 20 carbon atoms (aryl groups), or aromatic aliphatic groups having 7 to 25 carbon atoms (especially aralkyl groups, e.g., benzyl group (C6H5-CH2-)). In tertiary and quaternary amino groups, the remaining group bonded to the nitrogen atom may have an ethylenically unsaturated double bond. The cationic group may also be in salt form.

[0142] The cationic group, which is a salt, is a salt with an acid (organic 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, and stearic acid), are preferred. Dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate and their salts are preferred.

[0143] Specific examples of monomers having cationic groups 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., acetates) 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., acetates) 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 - SO3 Black3 CH2=C(CH3)COO-CH2CH2-N + (CH3)(-CH2-C6H5)2Br -

[0144] The ionic group-containing monomer (c) is preferably methacrylic acid, acrylic acid, or dimethylaminoethyl methacrylate, and more preferably methacrylic acid or dimethylaminoethyl methacrylate.

[0145] (d) Halogenated olefin monomers The vinyl polymer may have repeating units derived from the halogenated olefin monomer (d). The halogenated olefin monomer (d) does not need to have a fluorine atom. Preferably, the halogenated olefin monomer (d) is an olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine atoms, bromine atoms, or iodine atoms. Preferably, the halogenated olefin monomer (d) is a chlorinated olefin having 2 to 20 carbon atoms, and more preferably an olefin having 2 to 5 carbon atoms having 1 to 5 chlorine atoms. Preferred specific examples of halogenated olefin monomer (d) are halogenated vinyl, for example, vinyl chloride, vinyl bromide, vinyl iodide, and halogenated vinylidene, for example, vinylidene chloride, vinylidene bromide, and vinylidene iodide. Vinyl chloride or vinylidene chloride is preferred because it provides high water repellency (especially water repellency durability). The presence of repeating units derived from the halogenated olefin monomer (d) enhances the wash durability provided by the vinyl polymer.

[0146] (e) Crosslinkable monomers The vinyl polymer may contain repeating units derived from the crosslinkable monomer (e). The crosslinkable monomer (e) has a reactive group and / or an ethylenically unsaturated double bond (preferably a (meth)acrylate group). The crosslinkable monomer (e) may be a monomer that does not contain a fluorine atom. The crosslinkable monomer (e) may be a compound having at least two ethylenically unsaturated double bonds (preferably a (meth)acrylate group), or a compound having at least one ethylenically unsaturated double bond and at least one reactive group. Examples of reactive groups include hydroxyl groups, epoxy groups, chloromethyl groups, blocked isocyanate groups, amino groups, carboxyl groups, and the like.

[0147] Examples of crosslinkable monomers may be vinyl monomers having a reactive group, mono(meth)acrylates, di(meth)acrylates, or di(meth)acrylamides having a reactive group.

[0148] Examples of crosslinkable monomers include, but are not limited to, diacetone(meth)acrylamide, 3-chloro-2-hydroxypropyl(meth)acrylate, 2-acetoacetoxyethyl(meth)acrylate, butadiene, isoprene, chloroprene, vinyl monochloroacetate, vinyl methacrylate, glycidyl(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate.

[0149] (f) Cyclic hydrocarbon group-containing monomers The vinyl polymer may have repeating units derived from a cyclic hydrocarbon group-containing monomer (f). The cyclic hydrocarbon group-containing monomer (f) is a monomer having a cyclic hydrocarbon group, and may be a monomer having one ethylenically unsaturated double bond and a cyclic hydrocarbon group. The vinyl polymer may also be a styrene polymer having repeating units derived from styrene or a styrene derivative.

[0150] The cyclic hydrocarbon group-containing monomer (f) preferably has a (meth)acrylic group as the ethylenically unsaturated double bond, for example, it may have a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond.

[0151] The cyclic hydrocarbon group may be alicyclic or aromatic. The cyclic hydrocarbon group may be saturated or unsaturated. The cyclic hydrocarbon group may be monocyclic, polycyclic, or bridged ring group, with bridged ring group being preferred. The cyclic hydrocarbon group may have a chain-like group (for example, a halogen atom, a linear or branched hydrocarbon group (particularly a linear or branched hydrocarbon group having 1 to 20 carbon atoms)).

[0152] The number of carbon atoms in 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.

[0153] Specific examples of cyclic hydrocarbon groups 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 (e.g., cyclohexylene group, adamantylene group, phenylene group, naphthylene group, etc.), and substituted groups thereof.

[0154] Specific examples of cyclic hydrocarbon group-containing monomers (f) include cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, and compounds obtained by substituting these acrylates with acrylamide. These may be used alone or in combination of two or more.

[0155] An example of a cyclic hydrocarbon group-containing monomer (f) is a styrene compound. The styrene compound may be modified with a chain-like group (for example, a halogen atom, a linear or branched hydrocarbon group (particularly a linear or branched hydrocarbon group having 1 to 20 carbon atoms)). Specific examples include styrene, 4-t-butylstyrene, 3,5-di-t-butylstyrene, 2,4,6-tri-t-butylstyrene, 4-methylstyrene, 3,5-dimethylstyrene, 2,4,6-trimethylstyrene, etc. The styrene compound may be an α-methylstyrene compound or an α-chlorostyrene compound with a chlorine atom at the α-position, or a styrene compound with a hydrogen atom at the α-position.

[0156] (g) Polysiloxane group-containing monomer The vinyl polymer may have repeating units derived from a polysiloxane group-containing monomer (g). The monomer (g) has one ethylenically unsaturated double bond and a polysiloxane group.

[0157] The monomer (g) preferably has a (meth)acrylic group, and may, for example, have a (meth)acrylate group or a (meth)acrylamide group as an ethylenically unsaturated double bond.

[0158] The polysiloxane group present in monomer (g) is described in the above explanation of (polysiloxane group). Monomer (g) may have a polydimethylsiloxane group in its side chain.

[0159] The ethylenically unsaturated double bond and the polysiloxane group may be linked by any linker group.

[0160] The monomer (g) is, formula: CH2=C(-X g )-C(=O)-Y g (R) g k [In the formula, R g This is a group having a polydimethylsiloxane group, X g is a hydrogen atom, a monovalent organic group, or a halogen atom. Y g This is a group composed of at least one of the following: divalent to tetravalent carbon-1 hydrocarbon groups (especially -CH2-, -CH(-)2), -C6H4-, -O-, -C(=O)-, -S(=O)2-, or -NH-. k is between 1 and 3. It is preferable that the monomer is represented by .

[0161] X g This may be a hydrogen atom, a methyl group, a halogen other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. g Examples include hydrogen atoms, methyl groups, chlorine atoms, bromine atoms, iodine atoms, and cyano groups. g It is preferable that the element is a hydrogen atom, a methyl group, or a chlorine atom. g It is particularly preferable that it be a hydrogen atom.

[0162] Y g It is a divalent to tetravalent group. g It is preferable that the group is divalent. Y gIt is preferable that the group is composed of at least one of the following: a hydrocarbon group having 1 carbon atom, -C6H4-, -O-, -C(=O)-, -S(=O)2-, or -NH-. g It is preferable that it is not a hydrocarbon group. Examples of a C1 hydrocarbon group include -CH2-, -CH(-)2, or -C(-)3. A hydrocarbon group having C1 is repeated, and -(CH2) m -(m is an integer from 1 to 5) may form a hydrocarbon group with 2 or more carbon atoms. g It may have an NH group.

[0163] Y g -Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-R'-, -Y'-R'-Y'- , -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O)-Y'-, -Y'-R'-Y'-C(=O)-Y'-, or -Y'-R'-Y'-R'- [In the formula, Y' is a direct bond, -O-, -NH-, or -S(=O)2-, R' is -(CH2) m -(m is an integer between 1 and 5) or -C6H4- (phenylene group). That's fine.

[0164] Y g Specific examples are -O-, -NH-, -OC(=O)-, -C(=O)-NH-, -NH-C(=O)-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C6H4-, -O-(CH2) m -O-, -NH-(CH2) m -NH-, -O-(CH2) m -NH-, -NH-(CH2) m -O-, -O-(CH2) m -OC(=O)-, -O-(CH2) m -C(=O)-O-, -NH-(CH2) m -OC(=O)-, -NH-(CH2) m -C(=O)-O-, -O-(CH2) m-OC(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -C(=O)-NH-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -O-C6H4-, -O-(CH2) m -NH-S(=O)2-, -O-(CH2) m -S(=O)2-NH-, -NH-(CH2) m -OC(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -NH-C(=O)-NH-, -NH-(CH2) m -O-C6H4-, -NH-(CH2) m -NH-C6H4-, -NH-(CH2) m -NH-S(=O)2-, or -NH-(CH2) m The formula is -S(=O)2-NH- [wherein m is 1 to 5, especially 2 or 4].

[0165] Y g -O-, -NH-, -O-(CH2) m -OC(=O)-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -OC(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -NH-S(=O)2-, -O-(CH2) m -S(=O)2-NH-, -NH-(CH2) m -NH-S(=O)2-, or -NH-(CH2) m -S(=O)2-NH- [In the formula, m is an integer between 1 and 5, in particular 2 or 4.] It is preferable that this is the case.g is -O- or -O-(CH2) m -NH-C(=O)-, especially -O-(CH2) m -NH-C(=O)- is more preferable.

[0166] R g This refers to a group having a polydimethylsiloxane group, and the explanation of the polydimethylsiloxane group described above (polysiloxane group) is used for further details.

[0167] Examples of monomers (g) are as follows: CH2=C(-X g )-C(=O)-Y g -[-Si(R s )2-O-] a -Si(R s )3 CH2=C(-X g )-C(=O)-Y g -L s1 -[-Si(R s )2-O-] a -Si(R s )3 CH2=C(-X g )-C(=O)-Y g -L s1 -OL s1 -[-Si(R s )2-O-] a -R s CH2=C(-X g )-C(=O)-Y g -L s1 -[-Si(R s )2-O-] a -Si(R s )3 CH2=C(-X g )-C(=O)-Y g -L s1 -OL s1 -[-Si(R s )2-O-] a -R s CH2=C(-X g )-C(=O)-Y g -L s1-[-Si(R s )2-O-] a -Si(R s )3 CH2=C(-X g )-C(=O)-Y g -L s1 -[-Si(R s )2-O-] a -R s [In the formula, each symbol is interpreted as described above.]

[0168] (h) Other monomers Other monomers are not limited to these examples and include acrylonitrile, short-chain alkyl (meth)acrylates, vinyl acetate, vinyl alkyl ethers, etc. Other monomers (h) may be used alone or in combination of two or more.

[0169] [Composition of polymer] The combinations of monomers (a) to (g) that constitute the repeating unit of the vinyl polymer are not particularly limited, but for example, they are as follows (parentheses omitted). a a+ a+b+c a+c a+d a+b+c+d a+b+c+d+e a+b+c+d+e+f In the above combinations, monomer (g) may be used in place of monomer (a) or in addition to monomer (a). Other monomers (g) may also be used in combination with the above combinations. For pulp products, it is preferable to use monomers (a), (b), and (c) in combination.

[0170] The amount of repeating units derived from monomer (a) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, relative to the vinyl polymer, and may also 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.

[0171] The amount of monomer (a) (especially monomer (a1)) relative to the vinyl polymer may be more than 90% by weight, 92% or more by weight, 94% or more by weight, 96% or more by weight, 98% or more by weight, 99% or more by weight, 99.5% or more by weight, or 100% by weight, for example, 93% or more by weight, preferably more than 97% by weight, and also 100% or less by weight, 99% or less by weight, 97% or less by weight, 95% or less by weight, or 93% or less by weight, and in one embodiment, more than 90% by weight and 100% or less by weight. The amount of monomer (a1) relative to the vinyl polymer may be 100% by weight.

[0172] Of the monomer (a), the amount of monomer (a1) 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, preferably 30% by weight or more, and may also be 100% by weight or less, 90% by weight or less, 80% by weight or less, 50% by weight or less, or 30% by weight or less.

[0173] Of monomer (a), the amount of 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 may also be 100% by weight or less, 90% by weight or less, 80% by weight or less, 50% by weight or less, or 30% by weight or less.

[0174] The amount of repeating units derived from monomer (b) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, and may also 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. The amount of repeating units derived from monomer (b) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may also be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of repeating units derived from monomer (a).

[0175] The amount of repeating units derived from monomer (c) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, relative to the vinyl polymer, and may also 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. The amount of repeating units derived from monomer (c) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may also be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of repeating units derived from monomer (a).

[0176] The amount of repeating units derived from monomer (d) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, relative to the vinyl polymer. Alternatively, the amount of repeating units derived from monomer (d) may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, relative to the vinyl polymer. The amount of repeating units derived from monomer (d) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, relative to 100 parts by weight of repeating units derived from monomer (a). Alternatively, it 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.

[0177] The amount of repeating units derived from monomer (e) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, relative to the vinyl polymer, and may also 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. The amount of repeating units derived from monomer (e) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may also be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of repeating units derived from monomer (a).

[0178] The amount of repeating units derived from monomer (f) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, and may also 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. The amount of repeating units derived from monomer (f) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may also be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of repeating units derived from monomer (a).

[0179] The amount of repeating units 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, and may also 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. The amount of repeating units derived from the monomer (g) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may also be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of repeating units derived from the monomer (a).

[0180] The amount of repeating units derived from the monomer (h) 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, and may also 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. The amount of repeating units derived from monomer (h) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may also be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of repeating units derived from monomer (a).

[0181] When monomer (g) is used instead of monomer (a), the phrase "100 parts by weight of repeating units derived from monomer (a)" in the above description of the quantities of each monomer may be read as "100 parts by weight of repeating units derived from monomer (g)."

[0182] [Polymerization method] Vinyl polymers can be produced by known polymerization methods, and the conditions for the polymerization reaction can be arbitrarily selected. Examples of such polymerization methods include solution polymerization, suspension polymerization, emulsion polymerization, and condensation polymerization.

[0183] In solution polymerization, monomers are dissolved in an organic solvent in the presence of a polymerization initiator, followed by nitrogen purging and heating and stirring at a temperature of 30 to 120°C for 1 to 10 hours. Examples of polymerization initiators include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight, per 100 parts by weight of monomer.

[0184] Organic solvents are inert to monomers and dissolve them, and may include, for example, esters (e.g., esters with 2 to 40 carbon atoms, specifically ethyl acetate and butyl acetate), ketones (e.g., ketones with 2 to 40 carbon atoms, specifically methyl ethyl ketone, diisobutyl ketone, and methyl isobutyl ketone), and alcohols (e.g., alcohols with 1 to 40 carbon atoms, specifically ethanol, butanol, and isopropyl alcohol). Specific examples of organic solvents include acetone, chloroform, HCFC-225, isopropyl alcohol, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, and trichlorotrifluoroethane. The organic solvent is used in an amount of 10 to 3000 parts by weight, for example, 50 to 2000 parts by weight, per 100 parts by weight of the total monomers.

[0185] In emulsion polymerization, a method is employed in which monomers are emulsified in water in the presence of a polymerization initiator and an emulsifier, and then polymerized by stirring at a temperature of 50-80°C for 1-20 hours after nitrogen purging. Polymerization initiators include 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, and ammonium persulfate, as well as oil-soluble ones such as azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount of 0.01-10 parts by weight per 100 parts by weight of monomer.

[0186] To obtain a polymer aqueous dispersion with excellent stability during storage, it is desirable to polymerize the monomers by micronizing them in water using an emulsifying device that can impart strong crushing energy, such as a high-pressure homogenizer or an ultrasonic homogenizer. Various emulsifiers, including anionic, cationic, and nonionic types, can be used as emulsifiers, typically in an amount ranging from 0.5 to 20 parts by weight per 100 parts by weight of monomer. It is preferable to use anionic and / or nonionic and / or cationic emulsifiers. If the monomers are not completely miscible, it is preferable to add a compatibilizer that allows them to be sufficiently miscible, such as a water-soluble organic solvent or a low molecular weight monomer. Adding a compatibilizer can improve emulsifying and copolymerizing properties.

[0187] As the water-soluble organic solvent, the organic solvents mentioned above 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 used in a range of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, per 100 parts by weight of water. In addition, as low molecular weight monomers, methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, etc., may be used in a range of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, per 100 parts by weight of the total amount of monomers.

[0188] In polymerization, a chain transfer agent may be used. The molecular weight of the polymer can be changed depending on the amount of chain transfer agent used. Examples of chain transfer agents include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (especially alkyl mercaptans (e.g., with 1 to 40 carbon atoms)), and inorganic salts such as sodium hypophosphite and sodium bisulfite. The amount of chain transfer agent used may be in the range of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, per 100 parts by weight of the total amount of monomer.

[0189] [Amine-modified] As an example of a liquid-repellent compound, amine-modified compounds will be described. Amine-modified compounds are compounds that have been chemically modified to exhibit liquid-repellent properties from an amine compound.

[0190] The amine-modified compounds in this disclosure exhibit excellent dispersibility in liquid media due to their structure, and the repellents in this disclosure can have stable performance. In the case of repellents using polymer-type compounds as active ingredients, the molecular weight distribution is broad and tends to contain a relatively large amount of impurity components. On the other hand, amine-modified compounds can be reduced in molecular weight, narrowing (single-molecule) the molecular weight distribution, and thus can have good performance.

[0191] [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, and may also 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.

[0192] The amine-modified compounds in this disclosure do not necessarily have active hydrogen-containing groups. Examples of active hydrogen-containing groups include amino groups (amino groups not adjacent to a carbonyl group, e.g., primary or secondary amino groups), hydroxyl groups, and carboxyl groups. In particular, the amine-modified compounds in this disclosure do not necessarily have primary or secondary amino groups not adjacent to a carbonyl group.

[0193] The amine-modified product in this disclosure may be a polyamide having multiple amide structures, for example, an amine (a starting amine compound, e.g., a polyamine) with multiple modifying groups (e.g., Z as described below) N The polyamide may be modified via an amide structure. Here, the amide may be an amide structure contained in urethane groups, urea groups, imides, etc.

[0194] The amine-modified compound may be a compound obtained by modifying an amine (starting amine compound) with a hydrocarbon group having 6 or more carbon atoms, or a polysiloxane group, which may have substituents.

[0195] The amine-modified compound has one or more amino groups of the amine substituted with a modifying group. The modifying group is preferably a hydrocarbon group having 6 or more carbon atoms, which may have substituents, or a polysiloxane group, and is particularly preferably a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have substituents, or a monovalent polysiloxane group. From the viewpoint of improving liquid repellency, the amine-modified compound may have a structure in which the amine is modified with a monovalent aliphatic hydrocarbon group having 6 to 40 carbon atoms.

[0196] For details on hydrocarbon groups or polysiloxane groups having 6 or more carbon atoms that may have substituents, refer to the above-mentioned descriptions of (hydrocarbon groups having 6 or more carbon atoms that may have substituents) and (polysiloxane groups).

[0197] (Amine skeleton) The amine-modified compounds in this disclosure have an amine skeleton. The amine skeleton is obtained by removing a predetermined number of atoms or groups of atoms (e.g., hydrogen) from an amine compound and has one or more amino groups having a predetermined number of bonds (valence). The amino groups in the amine skeleton refer to groups selected from the group consisting of -NH2, -NH-, and -N(-)2, and also include amino groups adjacent to carbonyl groups contained in amide groups, urethane groups, urea groups, imides, etc. The amine skeleton may be any aliphatic or aromatic group having one or more amino groups, and the presence of heteroatoms other than nitrogen is not excluded.

[0198] 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, and may also 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.

[0199] The number of carbon atoms in the amine skeleton may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, and may also 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, and particularly 30 or less.

[0200] The amine skeleton has one or more amino groups. The amino groups are 1-3 valent amino groups, and are 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, and may also be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1.

[0201] The amine skeleton has hydrocarbon groups (aliphatic hydrocarbon groups or aromatic hydrocarbon groups). The hydrocarbon groups may be cyclic, branched, or linear. The hydrocarbon groups may be saturated or unsaturated (e.g., saturated). Here, the hydrocarbon groups may be cleaved by oxygen atoms and / or sulfur atoms, or they may consist only of carbon atoms, nitrogen atoms, and hydrogen atoms. The hydrocarbon groups may be hydrocarbon groups that are cleaved by oxygen atoms and / or sulfur atoms (e.g., linear saturated aliphatic hydrocarbon groups or aromatic hydrocarbon groups having 1-2 hydrocarbon aromatic rings), or they may be general hydrocarbon groups (e.g., linear saturated aliphatic hydrocarbon groups or aromatic hydrocarbon groups having 1-2 hydrocarbon aromatic rings). When the hydrocarbon groups are cleaved by oxygen atoms and / or sulfur atoms, they have an ether, thioether, polyether, or polythioether structure. The number of hydrocarbon groups in the amine skeleton may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, and may also be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1.

[0202] The amine skeleton may consist of a 1-3 valent amino group and a chain-like saturated aliphatic hydrocarbon group or aromatic hydrocarbon group, which may be cleaved by an oxygen atom and / or a sulfur atom.

[0203] 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, and may also 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.

[0204] (-Y N -Z N n ) The amine-modified product in this disclosure is given by the following formula: -Y N -Z N n [In the formula, Y Nis a directly bonded or 1+n valence group, Z N This is a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have substituents, or a monovalent polysiloxane group. n is an integer between 1 and 3 (inclusive). It has one or more bases represented by, At least one -Y N -Z N n However, it may be bonded to a nitrogen atom of the amine skeleton.

[0205] The amine-modified compound has -Y N -Z N n The number may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, preferably 2 or more, and may also be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1.

[0206] At least one -Y in the amine-modified product N -Z N n However, it is bonded to the nitrogen atom of the amine skeleton. All -Y in amine-modified products N -Z N n Of the number of -Y atoms bonded to the nitrogen atom of the amine skeleton N -Z N n The proportion of these may be 10% or more, 30% or more, 60% or more, 80% or more, or 100%, and may also be 100% or less, 95% or less, 75% or less, 50% or less, or 25% or less. -Y not bonded to the nitrogen atom of the amine skeleton N -Z N n It may be bonded to other groups (e.g., hydrocarbon groups) of the amine skeleton.

[0207] (Y N ) Y N is a directly bonded or 1+n valence group, preferably a 1+n valence group. N It consists of an amine skeleton and n ZN It functions as a linker that connects them.

[0208] n is Y N Z that combines with N n is a number and may be an integer between 1 and 3, inclusive. n may be 1 or greater, 2 or greater, or 3 or greater, and may also be 3 or less, 2 or less, or 1 or less, for example, 2 or less.

[0209] Y N This may be an aliphatic group (unsaturated aliphatic group or saturated aliphatic group) or an aromatic group.

[0210] Y N The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more, and may also be 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, or 300 or less.

[0211] Y N It may have a carbonyl group. N Y may have one or more selected from the group consisting of amide groups, urea groups, urethane groups, and imide groups, or N It may form one or more groups selected from the group consisting of amide groups, urea groups, urethane groups, and imide groups together with the amino group in the amine skeleton. Examples of such amide groups, urea groups, urethane groups, and imide groups are: -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'- -C(=O)-NR'- -C(=O)-NR'-C(=O)- [In the formula, R' is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms).] Y N Preferably, it is bonded to the nitrogen atom in the amine skeleton via a -(C=O)- group.

[0212] Y N These include direct bonds, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2, -N(-)2, 2-4 valent aliphatic hydrocarbon groups with 1-20 carbon atoms, 2-4 valent aromatic hydrocarbon rings, and 2-4 valent heterocycles. [In the formula, R' is 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).] It may be a 1+n valence base composed of one or more elements selected from the group consisting of the following:

[0213] Y N Y N1 and Y N2 A 1+n valence base consisting of one or more selected from the group comprising, Y N1 This 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 a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) in each occurrence). Y N2 This is a group composed of one or more selected from the group consisting of a di-tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a di-tetravalent aromatic hydrocarbon ring, and a di-tetravalent heterocycle. It may be a 1+n valency group consisting of one or more selected from the group consisting of . In this specification, Y N The groups described as such have an amine skeleton on the left and a Z group on the right. N Combine.

[0214] 〇 Y N1 Y N1 It is a non-hydrocarbon linker.

[0215] Y N1 This is a directly bonded or divalent or more group. N1The valence of Y may be 2-4, 2-3, or 2. N1 It is preferable that the bonding is not solely direct.

[0216] Y N1 The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and may also be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0217] Y N1 It may consist 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 a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) in each occurrence). N1 Examples include, direct binding, -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -C(=O)-NR'-C(=O)-, -C(=NR')-, -S-, -SO2-, -SO2NR'-, -C(OR')R'-, -C(OR')(-)2, -N(-)2 etc. [In the formula, R' is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) in each instance.] This is one example. Furthermore, Y N1 If a nitrogen atom is bonded to a nitrogen atom of the amine skeleton, that nitrogen atom is considered part of the amine skeleton (amino group).

[0218] 〇 Y N2 Y N2 This is a linker of an optionally substituted hydrocarbon, an optionally substituted hydrocarbon aromatic ring, or an optionally substituted heterocycle.

[0219] Y N2 Y may be a hydrocarbon group or a non-hydrocarbon group (including heteroatoms). N2 Y may be aliphatic or aromatic. N2 The chain may be linear, branched, or annular.

[0220] Y N2 Y is a group with two or more valent values. N2 The valence may be, for example, 2-4, 2-3, or 2.

[0221] Y N2 The number of carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, and may also 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.

[0222] Y N2 It consists of one or more selected from the group consisting of a di- to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have substituents, a di- to tetravalent hydrocarbon aromatic ring which may have substituents, and a di- to tetravalent heterocycle which may have substituents.

[0223] A divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or linear hydrocarbon group. A 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 in a divalent 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, and may also be 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less. The valency of the aliphatic hydrocarbon group may be 2 or more, 3 or more, or 4, and may also be 4 or less, 3 or less, or 2.

[0224] Aliphatic hydrocarbon groups may have substituents. Examples of substituents include -OR', -N(R')2, -COOR', and halogen atoms (wherein 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 in each occurrence). Substituents may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In a substituted aliphatic hydrocarbon group, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0225] Examples of divalent to tetravalent hydrocarbon aromatic rings include groups obtained by removing 2 to 4 hydrogen atoms from hydrocarbon aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthacene), pentacene, pyrene, and coronene. The number of ring constituent atoms of the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valency of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0226] The hydrocarbon aromatic ring may have substituents. Examples of substituents include -R', -OR', -N(R')2, -COOR', and halogen atoms (wherein 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 in each occurrence). The substituents may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the 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, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0227] The 2-4 valent heterocycle may be an aliphatic group or an aromatic group. Examples of 2-4 valent heterocycles include groups obtained by removing 2-4 hydrogen atoms from pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, etc. The number of ring constituent atoms of the heterocycle is 3-20, 4-16, or 5-12, preferably 5-12. The valency of the heterocycle may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0228] The heterocycle may have substituents. Examples of substituents include -R', -OR', -N(R')2, -COOR', and halogen atoms (wherein 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 in each occurrence). The substituents may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In a substituted heterocycle, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, for example, 65 mol% or more, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less.

[0229] Y N2 Examples include, -Ali- -Cy- -Ali(-)2 -Cy(-)2 (-)2Ali- (-)2Cy- (-)2Ali(-)2 (-)2Cy(-)2 -Ali-Cy- -Cy-Ali- -Cy-Ali-Cy- -Ali-Cy-Ali- [In the formula, Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and Cy is a hydrocarbon aromatic ring or heterocycle.] These are some examples.

[0230] Y N2 Specific examples include: -(CH2) p -(p is 1-40, 1-20, or 1-10), A linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and unsaturated bonds. 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 between 0 and 20, for example between 1 and 10, and Cy is a hydrocarbon aromatic ring or heterocycle) These are some examples.

[0231] ·Y N Examples Y N Let's explain an example. In the following, R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms) in each instance.

[0232] Y N An example is Y N If it is divalent, -Y N1 -, -Y N1 -Y N2 -, -Y N1 -Y N2 -Y N1 -, -Y N1 -Y N2 -Y N1 -Y N2 -, -Y N2 -, -Y N2 -Y N1 -, -Y N2 -Y N1 -Y N2 -, -Y N2 -Y N1 -Y N2 -Y N1 -, etc. are examples.

[0233] Y N An example is Y N If it 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 -YN1 -), 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, -Y N2 -Y N1 -Y N2 -Y N1 (-), 2, -Y N2 -Y N1 -Y N2 -(Y N1 -) 2、 -Y N2 -Y N1 -(Y N2 -Y N1 -) 2、 -Y N2 -(Y N1 -Y N2 -Y N1 -), 2, etc. can be mentioned.

[0234] Y N As an example of Y N when it is tetravalent, -Y N1 (-), 3, -Y N1 -Y N2 (-), 3, -Y N1 -(YN2 -)3, -Y N1 -Y N2 -Y N1 (-)3, -Y N1 -Y N2 (-Y N1 -)3, -Y N1 -(Y N2 -Y N1 -)3, -Y N1 -Y N2 -Y N1 -Y N2 (-)3, -Y N1 -Y N2 -Y N1 -(Y N2 -) 3、 -Y N1 -Y N2 -(Y N1 -Y N2 -) 3、 -Y N1 -(Y N2 -Y N1 -Y N2 -)3; -Y N2 (-)3, -Y N2 -Y N1 (-)3, -Y N2 -(Y N1 -)3, -Y N2 -Y N1 -Y N2 (-)3, -Y N2 -Y N1 (-Y N2 -)3, -Y N2 -(Y N1 -Y N2 -)3, -Y N2 -Y N1 -Y N2 -Y N1 (-)3, -Y N2 -Y N1 -Y N2 -(Y N1 -) 3、 -Y N2 -Y N1 -(Y N2 -Y N1 -) 3、 -Y N2 -(Y N1 -Y N2 -Y N1 -)3; etc. can be mentioned.

[0235] Y N A preferred example of this is -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, Examples include: In the amine-modified product, one or more Y N However, it is preferable that the amine skeleton-side terminal is -(C=O)- and that it is bonded to a nitrogen atom in the amine skeleton.

[0236] Y N Preferably, -Y N1 -, -Y N1 -Y N2 -, -Y N1 -Y N2 -Y N1 -, -Y N1 -Y N2 (-)2, -Y N2 -, -Y N2 -Y N1 -, -Y N2 -Y N1 -Y N2 -, -Y N2 -Y N1 (-)2, [In the formula, Y N1 However, in each appearance independently, direct binding, -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, or -C(=O)-NR'- -C(=O)-NR'-C(=O)- (In the formula, R' is independently 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) in each instance.) And, Y N2 This is a divalent to tetravalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, or a divalent aromatic group (e.g., a divalent phenyl group, a divalent triazole group). This is a group represented by [formula]. This allows for good liquid repellency to be imparted to the substrate.

[0237] Y N Further examples include: *-(C=O)- -O-(C=O)-NR'- [In the formula, * means that it is bonded to the nitrogen atom of the amine skeleton.] R' is either a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms). These are some examples.

[0238] (Z N ) Z N This is a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have substituents, or a monovalent polysiloxane group, and the above-mentioned explanations of (hydrocarbon groups having 6 or more carbon atoms, which may have substituents) and (polysiloxane groups) are used as reference.

[0239] [Examples of amine-modified compounds] (Amine-modified example 1) An example of an amine-modified compound is shown below: N(-Y N -Z N n ) p (New H) q -L1 -[N(-Y N -Z N n ) r (New H) s -L 1 -] t -N(-Y N -Z N n ) p (New H) q [In the formula, Y N In each occurrence, independently, it is either a direct bond or a 1+n valence base. Z N In each instance, independently, it is a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have substituents. L 1 This is a divalent aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms, which may be independently cleaved by oxygen atoms and / or sulfur atoms in each appearance. n is an integer between 1 and 3, independently of each occurrence. p is an integer between 0 and 2, independently in each occurrence. q is an integer between 0 and 2, independently in each occurrence. p+q is each N(-Y N -Z N n ) p (New H) q In this case, it is 2, r is either 0 or 1 independently in each occurrence. s is independently 0 or 1 in each occurrence. r+s is each N(-Y N -Z N n ) r (New H) s In this case, it is 1, The sum of all p and all r is 1 or greater. t is an integer between 0 and 10 (inclusive). Examples of compounds represented by (Amine Modified Compound Example 1) include the following.

[0240] In amine-modified example 1, Y N , Z N For details regarding , and n, please refer to the explanation above.

[0241] In amine-modified example 1, L 1 L is a divalent aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms, which may be cleaved by oxygen atoms and / or sulfur atoms, and may be a cyclic, branched, or linear hydrocarbon group, preferably a linear hydrocarbon group or an aromatic hydrocarbon. 1 As an example, the hydrocarbon group described above in the explanation of the [amine skeleton] may be used, and the hydrocarbon group may be divided by an oxygen atom and / or a sulfur atom, or it may consist only of a carbon atom, a nitrogen atom, and a hydrogen atom. 1 This may be, for example, a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1-2 hydrocarbon aromatic rings. 1 However, it is preferable that the cyclic group has both a ring (e.g., an aromatic ring) and a chain-like structure (e.g., a linear structure, ether oxygen, thioether sulfur), and specific examples include 1,3-phenylenebisalkylene group, 1,4-phenylenebisalkylene group, diphenyletherdiyl group, diphenylthioetherdiyl group, etc. 1 The number of carbon atoms may be 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more, and may also 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.

[0242] In amine-modified example 1, p is an integer between 0 and 2, independently in each occurrence, and q is an integer between 0 and 2, independently in each occurrence, and p+q is each N(-Y N -Z N n ) p (New H) q In this case, it is 2. Preferably, p may be 1 or greater in each occurrence independently, for example, 2.

[0243] In amine-modified example 1, r is independently 0 or 1 in each occurrence, s is independently 0 or 1 in each occurrence, and r+s is each N(-Y N -Z N n ) r (New H) s In this case, it is 1. Preferably, p may be 1 or greater in each occurrence independently, for example, 2.

[0244] The sum of all p and all r is 1 or greater, that is, amine-modified example 1 has one or more -Y N -Z N n The sum of all p and all r may be 1 or greater, 3 or greater, 5 or greater, 7 or greater, 9 or greater, or 12 or greater (the sum of all q and all s may be 0), and may be 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, or 4 or less.

[0245] In amine-modified example 1, t is an integer between 0 and 10. t may be 0 or greater, 1 or greater, 2 or greater, 4 or greater, or 6 or greater, preferably 0 or greater or 2 or greater, and t may be 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1 or less, for example, 0 or 1.

[0246] (Amine-modified example 2) Examples of other amine-modified compounds include the following formula: N(-Y N -Z N n ) p (New H) q -L 2 (-Y N -Z N n ) u [In the formula, Y N In each occurrence, independently, it is either a direct bond or a 1+n valence base. Z N In each instance, independently, it is a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have substituents. L2 This is a 1+u valent aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms, which may be cleaved by oxygen atoms and / or sulfur atoms. n is an integer between 1 and 3, independently of each occurrence. p is an integer between 0 and 2, q is an integer between 0 and 2, p+q is 2, u is an integer between 1 and 3, The sum of p and u is 1 or greater. A compound represented by (Amine Modified Compound Example 2) is an example.

[0247] In amine-modified example 2, Y N , Z N For details regarding n, please refer to the explanation above.

[0248] In amine-modified example 2, L 2 L is a 1+u valent aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms, which may be cleaved by oxygen atoms and / or sulfur atoms, and may be a cyclic, branched, or linear hydrocarbon group, preferably a linear hydrocarbon group or an aromatic hydrocarbon. 2 As an example, the hydrocarbon group described above in the explanation of the [amine skeleton] may be used, and the hydrocarbon group may be divided by an oxygen atom and / or a sulfur atom, or it may consist only of a carbon atom, a nitrogen atom, and a hydrogen atom. 2 This may be, for example, a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1-2 hydrocarbon aromatic rings. 2 However, it is preferable that the cyclic group has both a ring (e.g., an aromatic ring) and a chain-like structure (e.g., a linear structure, ether oxygen, thioether sulfur), and specific examples include 1,3-phenylenebisalkylene group, 1,4-phenylenebisalkylene group, diphenyletherdiyl group, diphenylthioetherdiyl group, etc. 2The number of carbon atoms may be 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more, and may be 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, or 3 or less.

[0249] In amine-modified example 2, p is an integer between 0 and 2, q is an integer between 0 and 2, and p+q is 2. Preferably, p may be 1 or greater, for example, 2.

[0250] In amine-modified example 2, u is an integer between 1 and 3. u is 1, 2, or 3, for example, 2 or 3.

[0251] In amine-modified example 2, the sum of p and u is 1 or more, meaning that amine-modified example 2 has one or more -Y N -Z N n The sum of all p and u may be 1 or greater, 2 or greater, 3 or greater, 4 or greater, or 5 or greater (the sum of all q may be 0), and the sum of p and u may be 5 or less, 4 or less, 3 or less, or 2 or less.

[0252] (Specific example) A specific example of an amine-modified compound is the compound represented by the following formula. For details on Z in the following formula, see the explanation above. N We will use this as a reference.

[0253] TIFF0007832566000015.tif4050

[0254] TIFF0007832566000016.tif3568

[0255] TIFF0007832566000017.tif4746

[0256] TIFF0007832566000018.tif2844

[0257] TIFF0007832566000019.tif2664

[0258] TIFF0007832566000020.tif2554

[0259] TIFF0007832566000021.tif2765

[0260] Amine-modified compounds may be synthetic waxes derived from animal or vegetable oils. Synthetic waxes may be obtained by condensing fatty acids derived from animal or vegetable oils with aliphatic or aromatic amines. Examples of synthetic waxes include fatty acid amide compounds such as hydroxy fatty acid amides, palmitic acid amides, octadecanoic acid amides, stearic acid amides, arachidinic acid amides, behenic acid amides, lignoceric acid amides, oleic acid amides, linoleic acid amides, α-linolenic acid amides, γ-linolenic acid amides, arachidonic acid amides, eicosapentaenoic acid amides, and docosahexaenoic acid amides.

[0261] [Manufacturing method] The method for producing amine-modified products is not limited to the above, but may involve using various amines (starting amines) and, if necessary, in the presence of a condensing agent, Z N A method of synthesis by reacting group-containing carboxylic acids, Z for various amines. N Methods for synthesis include reacting carboxylic acid acid chlorides, acid anhydrides, isocyanates, etc., that contain the group. The condensing agent may be any known condensing agent, such as DCC, EDCI, CDI, BOP, COMU, DMT-MM, DPPA, Py-Bop, etc.

[0262] (Amine (raw material amine)) Examples of amines (starter amines) that are precursors to the amine skeleton include alkylamines such as methylamine, ethylamine, propylamine, butylamine, and dibutylamine; alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, pentanediamine, hexamethylenediamine, cyclohexanediamine, and methylenebiscyclohexylamine; diethylenetriamine, triethylenetetramine, tris(2-aminoethyl)amine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripylenetetramine, tris(2-aminopropyl)amine, tetrapropylenepentamine, pentapropylenehexamine, iminobispropylamine, dibutylentriamine, bis(2-aminoethoxy)ethane, bis(2-aminoethyl) ether, bis[2-(2-aminoethoxy)ethyl] ether, and bis[2-(3-aminoprotoxy)ethyl] Polyalkylene polyamines such as ether, spermine, and spermidine; oxygen or sulfur-containing aliphatic amines such as 1-aminopropanediol, 2-amino-1,3-propanediol, 3-amino-1,2-propanediol, polyoxypropylenediamine, and polyoxyethylenediamine; aromatic monoamines such as aniline, 1- or 2-naphthylamine, 1-, 2- or 9-aminoanthracene, 9-aminophenanthracene, and 2-, 3- or 4-aminobiphenyl; monocyclic aromatic polyamines such as o-, m- or p-phenylenediamine, o-, m- or p-xylylenediamine, diaminotoluene, and 2,3-, 2,4- or 2,5-tolylenediamine;Diaminobiphenyl, bisaminophenoxyphenylpropane, diaminodiphenyl ether, diaminodiphenyl sulfide, diaminodiphenyl sulfone, diaminobenzophenone, diaminodiphenylmethane, diaminophenylpropane, diaminophenylhexafluoropropane, 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, Polycyclic aromatic polyamines such as diaminoaryloxybenzophenone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diaminotriphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-methylenebisaniline, 4,4'-oxydianiline, 1,3-bis(4-aminophenoxy)benzene, 4,4'-diaminodiphenyl ether, and 4,4'-bis(aminophenyl)amine; oxygen or sulfur-containing polycyclic aromatic polyamines such as 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 3,4'-diaminodiphenyl ether, and 4,4'-diaminodiphenyl sulfide;Examples include hydroxyl group-containing polyamines such as 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, and di-2-hydroxypropylethylenediamine. The polyamine may also be obtained by polymerizing polymerizable compounds such as allylamine.

[0263] [Polyol-modified compounds] As an example of a liquid-repellent compound, a polyol-modified compound will be described. A polyol-modified compound is a compound obtained by chemically modifying a polyol to exhibit liquid-repellent properties. The modifying group is preferably a hydrocarbon group having 6 or more carbon atoms, or a polysiloxane group, which may have substituents, and is particularly preferably a monovalent hydrocarbon group having 6 to 40 carbon atoms, or a monovalent polysiloxane group, which may have substituents. From the viewpoint of improving liquid repellency, the polyol-modified compound may have a structure in which a monovalent aliphatic hydrocarbon group having 6 to 40 carbon atoms is modified on the polyol.

[0264] For details on hydrocarbon groups or polysiloxane groups having 6 or more carbon atoms that may have substituents, refer to the above-mentioned descriptions of (hydrocarbon groups having 6 or more carbon atoms that may have substituents) and (polysiloxane groups).

[0265] [Structure etc.] The polyol-modified polymer may be a polymer with a degree of polymerization of 1 or more. From the viewpoint of improving liquid repellency, the degree of polymerization of the polyol-modified polymer may be 2 or more, 3 or more, 5 or more, 6 or more, preferably 7 or more, more preferably 8 or more, and even more preferably 9 or more. From the viewpoint of improving the handling of the repellent, it may be 100 or less, preferably 50 or less, more preferably 30 or less, and even more preferably 15 or less. The degree of polymerization refers to the number of repeating monomer units that make up the polymer.

[0266] In this disclosure, the degree of polymerization refers to the average degree of polymerization. In this disclosure, the average degree of polymerization refers to polymerization obtained by measurement under the following conditions. In this disclosure, when the polyol-modified product is a polyglycerin-modified product obtained by modifying polyglycerin, the degree of polymerization of the polyol-modified product refers to the average degree of polymerization of the polyglycerin. The average degree of polymerization of polyglycerin 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 (Equation 2) Hydroxyl value = 56110(n+2) / average molecular weight The hydroxyl value in (Equation 2) above is a numerical value that serves as an indicator of the magnitude of the number of hydroxyl groups contained in polyglycerin. The hydroxyl value is calculated from the amount of potassium hydroxide required to neutralize the acetic acid necessary to acetylate the free hydroxyl groups contained in 1 g of polyglycerin, and is calculated in accordance with the "Standard Oil and Fats Analysis Test Method (I), 2003 Edition," compiled by the Japan Oil Chemists' Society. The hydroxyl value of the raw material polyglycerin can be measured according to the above standard oil and fat analysis test method, and the average degree of polymerization and average molecular weight of polyglycerin can be calculated from the above relationship.

[0267] In the case where the polyol-modified product in this disclosure is a polyvinyl alcohol-modified product obtained by modifying polyvinyl alcohol, the degree of polymerization of the polyol-modified product refers to the average degree of polymerization of the polyvinyl alcohol. The average degree of polymerization of polyvinyl alcohol can be measured in accordance with the JIS K 6726 polyvinyl alcohol test method.

[0268] In this disclosure, if the polyol-modified product is a polysaccharide-modified product obtained by modifying a polysaccharide, the degree of polymerization of the polyol-modified product refers to the average degree of polymerization of the polysaccharide. The average degree of polymerization of the polysaccharide can be analyzed as follows. The degree of polymerization is the number of monosaccharide units (fructose and glucose units) in the polysaccharide, and the average degree of polymerization is determined by taking the top peak among the peaks of each analytical result obtained by conventional analytical methods such as HPLC, GC, and HPAEC as the average degree of polymerization. For example, the measurement can be performed by using a column such as Shinwa Chemical's ULTRON PS-80N (8 × 300 mm) (solvent: water, flow rate: 0.5 ml / min, temperature: 50°C) or TOSOH's TSK-GEL G30000 PWXL (7.8 × 300 mm) (solvent: water, flow rate: 0.5 ml / min, temperature: 50°C) and a differential refractometer as the detector.

[0269] The polyol-modified compounds may be low molecular weight (e.g., weight-average molecular weight less than 1500, less than 1000, or 500 or less) and / or high molecular weight. The weight-average molecular weight of the polyol-modified product may be 100 or more, 200 or more, 300 or more, 400 or more, 500 or more, 1000 or more, 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more, and may also 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.

[0270] The substitution rate of hydroxyl groups in the polyol-modified product may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 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, and may also be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, or 15% or less, for example 95% or less. Here, the "substitution rate" means the proportion (mol%) of hydroxyl groups derived from the polyol that are modified, and may mean the proportion (mol%) of those modified by monovalent hydrocarbon groups having 6 to 40 carbon atoms or monovalent polysiloxane groups that may have substituents.

[0271] The remaining percentage of hydroxyl groups in the polyol-modified product may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, for example, 5% or more, or 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, "remaining percentage" means the proportion (mol%) of hydroxyl groups derived from the polyol that are not modified.

[0272] The number of modifying groups in the polyol-modified product may be 2 or more, 5 or more, 7 or more, 8 or more, 9 or more, 10 or more, 12 or more, 15 or more, 30 or more, or 50 or more, and may also 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 having 6 to 40 carbon atoms or a monovalent polysiloxane group, which may have substituents.

[0273] The equivalent amount of the modifying group in 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, and may also be 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, or 400 or less. This is the value obtained by dividing the weight-average molecular weight of the polyol-modified product by the number of modifying groups. Here, the modifying group is preferably a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have substituents, or a monovalent polysiloxane group.

[0274] In polyol-modified products, one or more hydroxyl groups of the polyol are substituted with a modifying group. The modifying group is preferably a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have substituents, or a monovalent polysiloxane group. From the viewpoint of improving liquid repellency, the polyol-modified product may also have a structure in which the polyol is modified with an aliphatic hydrocarbon group having 6 to 40 carbon atoms.

[0275] For details on monovalent hydrocarbon groups having 6 to 40 carbon atoms that may have substituents and monovalent polysiloxane groups, refer to the above-mentioned descriptions of (hydrocarbon groups with 6 or more carbon atoms that may have substituents) and (polysiloxane groups).

[0276] (-Y O -Z O n ) The polyol-modified polyols in this disclosure are those in which one or more hydroxyl groups of the polyol are given by the following formula: -Y O -Z O n [In the formula, Y O Y O1 and Y O2 A 1+n valence base consisting of one or more selected from the group comprising, Y O1This 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 a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) in each occurrence). Y O2 This group is composed of one or more selected from the group consisting of a di- to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have substituents, a di- to tetravalent hydrocarbon aromatic ring which may have substituents, and a di- to tetravalent heterocycle which may have substituents. Z O This is a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have substituents, or a monovalent polysiloxane group. n is an integer between 1 and 3 (inclusive). It may be substituted with a group represented by .

[0277] (Y O ) Y O Y O1 and Y O2 A 1+n valence base consisting of one or more selected from the group comprising, Y O1 This 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 a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) in each occurrence). Y O2 This group is composed of one or more selected from the group consisting of a di- to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have substituents, a di- to tetravalent hydrocarbon aromatic ring which may have substituents, and a di- to tetravalent heterocycle which may have substituents.

[0278] n is Y O Z that combines withO n is a number and may be an integer between 1 and 3, inclusive. n may be 1 or greater, 2 or greater, or 3 or greater, and may also be 3 or less, 2 or less, or 1 or less, for example, 2 or less.

[0279] Y O The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more, and may also be 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.

[0280] Y O It 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 sulfonurea group, a sulfonurethane group, or a sulfonimide group. For example, Y O This may include -C(=O)-NR'-, -C(=S)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'-, or -SO2NR'-. O The inclusion of these groups can improve liquid repellency.

[0281] ○ Y O1 Y O1 It is a non-hydrocarbon linker.

[0282] Y O1 This is a directly bonded or divalent or more group. O1 The valence of Y may be 2-4, 2-3, or 2. O1 It is preferable that the bonding is not solely direct.

[0283] Y O1 The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0284] YO1 It may consist 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 a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) in each occurrence). O1 Examples include, direct binding, -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO2-, -SO2NR'-, -C(OR')R'-, -C(OR')(-)2nd class (In the formula, R' is independently 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) in each instance.) These are some examples.

[0285] Y O1 It 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 sulfonurea group, a sulfonurethane group, or a sulfonimide group. For example, Y O2 It may contain -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'-, or -SO2NR'-. O1 The inclusion of these groups can improve liquid repellency.

[0286] ○ Y O2 Y O2 This is a linker of an optionally substituted hydrocarbon, an optionally substituted hydrocarbon aromatic ring, or an optionally substituted heterocycle.

[0287] Y O2 Y may be a hydrocarbon group or a non-hydrocarbon group (including heteroatoms). O2 Y may be aliphatic or aromatic. O2 The chain may be linear, branched, or annular.

[0288] Y O2 Y is a group with two or more valent values. O2 The valence may be, for example, 2-4, 2-3, or 2.

[0289] Y O2 The number of carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, and may be 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.

[0290] Y O2 It consists of one or more selected from the group consisting of a di- to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have substituents, a di- to tetravalent hydrocarbon aromatic ring which may have substituents, and a di- to tetravalent heterocycle which may have substituents.

[0291] A divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or linear hydrocarbon group. A 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 in a divalent 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, and may also be 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less. The valency 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.

[0292] Aliphatic hydrocarbon groups may have substituents. Examples of substituents include -OR', -N(R')2, -COOR', and halogen atoms (wherein 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 in each occurrence). Substituents may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In a substituted aliphatic hydrocarbon group, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0293] Examples of divalent to tetravalent hydrocarbon aromatic rings include groups obtained by removing 2 to 4 hydrogen atoms from hydrocarbon aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthacene), pentacene, pyrene, and coronene. The number of ring constituent atoms of the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valency of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0294] The hydrocarbon aromatic ring may have substituents. Examples of substituents include -R', -OR', -N(R')2, -COOR', and halogen atoms (wherein 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 in each occurrence). The substituents may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the 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, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0295] The 2-4 valent heterocycle may be an aliphatic group or an aromatic group. Examples of 2-4 valent heterocycles include groups obtained by removing 2-4 hydrogen atoms from pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, etc. The number of ring constituent atoms of the heterocycle is 3-20, 4-16, or 5-12, preferably 5-12. The valency of the heterocycle may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0296] The heterocycle may have substituents. Examples of substituents include -R', -OR', -N(R')2, -COOR', and halogen atoms (wherein 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 in each occurrence). The substituents may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In a substituted heterocycle, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, for example, 65 mol% or more, or 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less.

[0297] Y O2 Examples include, -Ali- -Cy- -Ali(-)2 -Cy(-)2 (-)2Ali- (-)2Cy- (-)2Ali(-)2 (-)2Cy(-)2 -Ali-Cy- -Cy-Ali- -Cy-Ali-Cy- -Ali-Cy-Ali- [In the formula, Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and Cy is a hydrocarbon aromatic ring or heterocycle.] These are some examples.

[0298] Y O2 Specific examples include: -(CH2) p -(p is 1-40, 1-20, or 1-10), A linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and unsaturated bonds. 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 between 0 and 20, for example between 1 and 10, and Cy is a hydrocarbon aromatic ring or heterocycle) These are some examples.

[0299] (Y O Example) Y O Let's explain an example. In the following, R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms) in each instance.

[0300] Y O An example is Y O If it is divalent, -Y O1 -, -Y O1 -Y O2 -, -Y O1 -Y O2 -Y O1 -, -Y O1 -Y O2 -Y O1 -Y O2 -, -Y O2 -, -Y O2 -Y O1 -, -Y O2 -Y O1 -Y O2 -, -Y O2 -Y O1 -Y O2 -Y O1 - are some examples.

[0301] Y O An example is Y O If it 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 -YO1 -)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, -Y O2 -Y O1 -Y O2 -Y O1 (-)2, -Y O2 -Y O1 -Y O2 -(Y O1 -) <00008​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​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<00's0918>-Y O2 -Y O1 -(Y O2 -), 3、 -Y O1 -Y O2 -(Y O1 -Y O2 -), 3、 -Y O1 -(Y O2 -Y O1 -Y O2 -), 3; -Y O2 (-), 3, -Y O2 -Y O1 (-), 3, -Y O2 -(Y O1 (-), 3, -Y O2 -Y O1 -Y O2 (-), 3, -Y O2 -Y O1 (-Y O2 (-), 3, -Y O2 -(Y O1 -Y O2 (-), 3, -Y O2 -Y O1 -Y O2 -Y O1 (-), 3, -Y O2 -Y O1 -Y O2 -(Y O1 -), 3、 -Y O2 -Y O1 -(Y O2 -Y O1 -), 3、 -Y O2 -(Y O1 -Y O2 -Y O1 -), 3, etc. can be mentioned.

[0303] Y O Preferred examples of -Y O1 -,-Y O1 -Y O2 -,-Y O1 -Y O2 -Y O1 -,-Y O1 -Y O2 (-)2, -Y O2 -,-Y O2 -Y O1 -,-Y O2 -Y O1 -Y O2 -,-Y O2 -Y O1 (-)2, etc. can be mentioned.

[0304] (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.

[0305] Y O11It is a non-hydrocarbon linker, and is either directly bonded or a divalent or more valent group.

[0306] Y O11 The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and may also be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0307] Y O11 The bond may be a direct bond, -C(=O)-, -C(=O)-NR'-, or -C(=S)-NR'-.

[0308] Y O21 This is a linker of a divalent hydrocarbon, which may be a hydrocarbon group having 1 to 40 carbon atoms.

[0309] Y O21 The number of carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, and may also 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.

[0310] Here, the hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or straight hydrocarbon group, and may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group.

[0311] Y O21 Specific examples include: -(CH2) p -(p is 1-40, 1-20, or 1-10), A linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and unsaturated bonds. 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 between 0 and 20, for example between 1 and 10, and Cy is a hydrocarbon aromatic ring or heterocycle) These are some examples.

[0312] Y O12 may be -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO2-, -SO2NR'-, -C(OR')R'-, or -C(OR')(-)2.

[0313] Y O12 It 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 sulfonurea group, a sulfonurethane group, or a sulfonimide group. For example, Y O12 It may be -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'-, or -SO2NR'-. C12 The inclusion of these groups can improve liquid repellency.

[0314] (Z O ) Z O This is a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have substituents, or a monovalent polysiloxane group, and the above-mentioned explanations of (hydrocarbon groups having 6 or more carbon atoms, which may have substituents) and (polysiloxane groups) are used as reference.

[0315] [Other modifying groups] The hydroxyl group of the polyol is -Y O -Z O n It may be substituted with other modifying groups. Examples of modifying groups include anionic groups and / or cationic groups.

[0316] Examples of anionic groups include monomers having a carboxyl group, a sulfonic acid group, or a phosphate group.

[0317] Examples of salts of anionic groups include alkali metal salts, alkaline earth metal salts, or ammonium salts, such as methylammonium salt, ethanolammonium salt, and triethanolammonium salt.

[0318] The cationic group is an amino group, preferably a tertiary amino group and a quaternary amino group. In a tertiary amino group, the two groups bonded to the nitrogen atom are preferably the same or different aliphatic group having 1 to 5 carbon atoms (especially alkyl groups), an aromatic group having 6 to 20 carbon atoms (aryl groups), or an aromatic aliphatic group having 7 to 25 carbon atoms (especially aralkyl groups, such as benzyl groups (C6H5-CH2-)). In a quaternary amino group, the three groups bonded to the nitrogen atom are preferably the same or different aliphatic group having 1 to 5 carbon atoms (especially alkyl groups), an aromatic group having 6 to 20 carbon atoms (aryl groups), or an aromatic aliphatic group having 7 to 25 carbon atoms (especially aralkyl groups, such as benzyl groups (C6H5-CH2-)). In both tertiary and quaternary amino groups, the remaining group bonded to the nitrogen atom may have a carbon-carbon double bond. The cationic group may also be in the form of a salt.

[0319] The cationic 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, and stearic acid), are preferred.

[0320] [Manufacturing method] Polyol-modified products may also be produced by reacting a modifying agent having a modifying group (or a precursor structure of a modifying group) with the hydroxyl group of a polyol.

[0321] (Polyol) A polyol is a compound having two or more hydroxyl groups and is a compound that serves as a raw material for polyol-modified products. A polyol is a compound that has two or more hydroxyl groups in its molecule. Polyols may be aliphatic or aromatic, but are preferably aliphatic.

[0322] The polyol may have ether bonds. Preferably, the polyol may have two or more ether bonds. Specifically, the polyol is preferably a compound having two or more hydroxyl groups and two or more ether bonds. In other words, the polyol is preferably a polyether having two or more hydroxyl groups.

[0323] If the polyol is a polymer, the repeating structure of the monomer units may contain hydroxyl groups and ether bonds.

[0324] The polyol may be low molecular weight (e.g., weight-average molecular weight less than 1000, 500 or less) and / or high molecular weight. The weight-average molecular weight of the polyol may be 50 or more, 100 or more, 300 or more, 500 or more, 1000 or more, 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 30000 or more, 300000 or more, or 500000 or more, and may also be 1000000 or less, 750000 or less, 500000 or less, 30000 or less, 50000 or less, 75000 or less, 50000 or less, 30000 or less, 10000 or less, 5000 or less, 30000 or less, 2000 or less, 1000 or less, or 500 or less.

[0325] The number of hydroxyl groups in a polyol may be 2 or more, 5 or more, 7 or more, 10 or more, 15 or more, 30 or more, 50 or more, or 100 or more, and may also 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.

[0326] The hydroxyl group equivalent of a polyol may be 20 or more, 40 or more, 60 or more, 80 or more, 100 or more, 120 or more, or 150 or more, and may also be 1000 or less, 800 or less, 600 or less, 400 or less, 200 or less, 100 or less, or 75 or less. The hydroxyl group equivalent of a polyol is the value obtained by dividing the weight-average molecular weight of the polyol by the number of hydroxyl groups.

[0327] Polyols may be natural products. These natural products may be high molecular weight natural products, low molecular weight natural products, or derivatives thereof. The above natural products also include compounds converted from microorganisms. Examples of polyols include monosaccharides, oligosaccharides, polysaccharides, sugar alcohols (reducing sugars), hydroxy acids, amino acids, vitamins, flavonols, hydroxy hydrocarbons, hydroxy group-containing compound polymers, polyether polyols, polymer polyols, polyester polyols, and other polyols.

[0328] Examples of monosaccharides include glucose, fructose, galactose, and xylose.

[0329] Examples of oligosaccharides include sucrose, cycloamylose, cyclodextrin, maltose, trehalose, lactose, and sucralose.

[0330] Examples of sugar alcohols (reducing sugars) include sorbitol, maltitol, erythritol, isomalt, lactitol, mannitol, xylitol, sorbitan, and lactitol.

[0331] Examples of polysaccharides include starch, cellulose, curdlan, pullulan, alginic acid, carrageenan, guar gum, chitin, chitosan, locust bean gum, kappa-carrageenan, iota-carrageenan, isomaltodextrin, gellan gum, and tamarind seed gum.

[0332] Examples of hydroxy acids include ascorbic acid, kojic acid, quinic acid, chlorogenic acid, and gluconic acid.

[0333] Examples of amino acids include glucosamine.

[0334] Examples of vitamins include ascorbic acid and inositol.

[0335] Examples of flavonols include catechins, quercetin, and anthocyanins.

[0336] Examples of hydroxy hydrocarbons include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, glycerin, trimethylolpropane, and trimethylolethane. Hydroxy hydrocarbons are hydrocarbons having a hydroxyl group and may be aromatic or aliphatic, but are preferably aliphatic. When referring to hydroxy hydrocarbons, it may also mean hydroxy hydrocarbons other than compounds included in other groups such as polysaccharides (other hydroxy hydrocarbons).

[0337] Examples of hydroxyl group-containing compound polymers include polyglycerin, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymer, hydroxypropyl (meth)acrylate polymer, and hydroxybutyl (meth)acrylate polymer.

[0338] Examples of polyether polyols include compounds obtained by addition polymerization of alkylene oxide to an initiator. Examples of initiators include compounds having two or more hydroxyl groups. Examples of initiators include propylene glycol, polypropylene glycol, ethylene glycol, polyethylene glycol, glycerin, polyglycerin, trimethylolpropane, triethanolamine, pentaerythritol, ethylenediamine, aromatic diamine, diethylenetriamine, sorbitol, and sucrose. Examples of alkylene oxides include ethylene oxide and propylene oxide. Polyether polyols obtained by addition polymerization of alkylene oxide to the above initiators are also called polyoxyalkylene polyols or oxyalkylene derivatives of polyols. Representative examples of polyether polyols include polyoxypropylenetriol obtained by addition polymerization of propylene oxide to glycerin, and polyoxypropylene polyglyceryl ether obtained by addition polymerization of propylene oxide to polyglycerin.

[0339] Examples of polymer polyols include compounds obtained by polymerizing a polyether polyol with an ethylenically unsaturated monomer in a polyether polyol. Examples of the ethylenically unsaturated monomer include acrylonitrile and styrene.

[0340] Examples of polyester polyols include compounds obtained by dehydration condensation of a compound having two or more carboxyl groups and a compound having two or more hydroxyl groups. Examples of compounds having two or more 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 their acid anhydrides. Examples of compounds having two or more hydroxyl groups include ethylene glycol, propylene glycol, propanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and polymers thereof.

[0341] (Modifier) The modifier is preferably a compound that is reactive with the polyol and has a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have substituents, or a monovalent polysiloxane group, as described above.

[0342] Examples of modifiers are as follows: Acid halide G(O=)CZ O Acid anhydride O(C(=O)-Z O )2 Carboxylic acid HO(O=)CZ O Isocyanate O=C=NZ O Thioisocyanate S=C=NZ O Epoxy (CH2OCH)CH2O-Z O Halogenated GZ O Amine H2N-Z O Hydroxy HO-Z O [In the formula, Z O As described above, G is a halogen atom (e.g., F, Cl, Br, or I).

[0343] Z in the structure of the modifier described above O This can be replaced with any group that constitutes the modifying group, for example, Z O This may be a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have substituents, or a group having a monovalent polysiloxane group, for example, Z O to -Y O -Z O n That is also acceptable.

[0344] Polyol-modified compounds may also be synthesized by reacting a polyol with a modifier. For example, a polyol-modified compound can be synthesized by reacting a modifier, such as an acid halogen compound, acid anhydride, or carboxylic acid, with the hydroxyl group of a polyol to form an ester bond. Alternatively, a polyol-modified compound can be produced by reacting a modifier, such as a halide or epoxy compound, with the hydroxyl group of a polyol to form an ether bond. The reaction conditions between the polyol and the modifier can be appropriately designed by those skilled in the art, depending on the desired product, by using a catalyst (e.g., an acid catalyst or a base catalyst), a condensing agent, etc.

[0345] [Polycarboxylic acid modified product] As an example of a liquid-repellent compound, polycarboxylic acid-modified compounds will be described. Polycarboxylic acid-modified compounds are compounds obtained by chemically modifying polycarboxylic acids to exhibit liquid-repellent properties.

[0346] [Structure etc.] The polycarboxylic acid modified compounds may be low molecular weight (e.g., weight-average molecular weight less than 1500, less than 1000, or 500 or less) and / or high molecular weight. The weight-average molecular weight of the polycarboxylic acid modified product may be 100 or more, 200 or more, 300 or more, 400 or more, 500 or more, 1000 or more, 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more, and may also 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.

[0347] 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 under the following apparatus and conditions. Separation column: SB-806M (8mm x 30mm, Shodex) Column temperature: 40℃ Mobile phase solvent: Deionized water Mobile phase flow rate: 1.0 mL / min Sample concentration: 0.5 wt% Injection volume: 50μL Detector: RI detector (Waters 2414, Waters Corporation)

[0348] The weight-average molecular weight (Mw), number-average molecular weight (Mn), and polydispersity (Mw / Mn) of polycarboxylic acid-modified compounds, on a polystyrene basis, may be determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as the eluent and Shodex KF400RL and KF400RH columns (polystyrene gel) manufactured by Showa Denko Corporation.

[0349] The substitution rate of hydroxyl groups of carboxyl groups in polycarboxylic acid modified products 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, and may also be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, or 15% or less, for example 95% or less. Here, the "substitution rate" refers to the percentage (mol%) of hydroxyl groups of carboxyl groups derived from polycarboxylic acids that are modified, and may refer to the percentage (mol%) of groups modified by monovalent hydrocarbon groups having 6 to 40 carbon atoms or monovalent polysiloxane groups, which may have substituents.

[0350] The remaining percentage of hydroxyl groups of carboxyl groups in polycarboxylic acid-modified products 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, or 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, "remaining percentage" means the proportion (mol%) of hydroxyl groups of carboxyl groups derived from polycarboxylic acid that are not modified.

[0351] The number of modifying groups in the polycarboxylic acid modified product may be 2 or more, 5 or more, 7 or more, 10 or more, 15 or more, 30 or more, or 50 or more, and may also 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 having 6 to 40 carbon atoms, which may have substituents, or a monovalent polysiloxane group.

[0352] The equivalent amount of the modifying group in 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, and may also be 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, or 400 or less. This is the value obtained by dividing the weight-average molecular weight of the polycarboxylic acid modified product by the number of modifying groups. Here, the modifying group is preferably a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have substituents, or a monovalent polysiloxane group.

[0353] The polycarboxylic acid modified product has one or more hydroxyl groups of the polycarboxylic acid substituted with a modifying group. The modifying group is preferably a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have substituents, or a monovalent polysiloxane group. From the viewpoint of improving liquid repellency, the polycarboxylic acid modified product may have an aliphatic hydrocarbon group having 6 to 40 carbon atoms relative to the polycarboxylic acid.

[0354] For details on monovalent hydrocarbon groups having 6 to 40 carbon atoms that may have substituents and monovalent polysiloxane groups, refer to the above-mentioned descriptions of (hydrocarbon groups with 6 or more carbon atoms that may have substituents) and (polysiloxane groups).

[0355] (-Y C -Z C n ) The polycarboxylic acid modified product in this disclosure is a polycarboxylic acid modified in which one or more hydroxyl groups of carboxyl groups of the polycarboxylic acid are given by the following formula: -Y C -Z C n [In the formula, Y C Y C1 and Y C2 A 1+n valence base consisting of one or more selected from the group comprising, Y C1This 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 a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) in each occurrence). Y C2 This group is composed of one or more selected from the group consisting of a di- to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have substituents, a di- to tetravalent hydrocarbon aromatic ring which may have substituents, and a di- to tetravalent heterocycle which may have substituents. Z C This is a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have substituents, or a monovalent polysiloxane group. n is an integer between 1 and 3 (inclusive). It may be substituted with a group represented by .

[0356] (Y C ) Y C Y C1 and Y C2 A 1+n valence base consisting of one or more selected from the group comprising, Y C1 This 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 a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) in each occurrence). Y C2 This group is composed of one or more selected from the group consisting of a di- to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have substituents, a di- to tetravalent hydrocarbon aromatic ring which may have substituents, and a di- to tetravalent heterocycle which may have substituents.

[0357] n is Y C Z that combines withC n is a number and can be an integer between 1 and 3. n can be 1 or greater, 2 or greater, or 3 or greater. n can be 3 or less, 2 or less, or 1 or less, for example, 2 or less.

[0358] Y C The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more, and may also be 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.

[0359] Y C It 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 sulfonurea group, a sulfonurethane group, or a sulfonimide group. For example, Y C It may be -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'-, or -SO2NR'-. C The inclusion of these groups can improve liquid repellency.

[0360] ○ Y C1 Y C1 It is a non-hydrocarbon linker.

[0361] Y C1 This is a directly bonded or divalent or more group. C1 The valence of Y may be 2-4, 2-3, or 2. C1 It is preferable that the bonding is not solely direct.

[0362] Y C1 The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and may also be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0363] Y C1It may consist 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 a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) in each occurrence). C1 Examples include, direct binding, -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO2-, -SO2NR'-, -C(OR')R'-, -C(OR')(-)2nd class (In the formula, R' is independently 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) in each instance.) These are some examples.

[0364] Y C1 It 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 sulfonurea group, a sulfonurethane group, or a sulfonimide group. For example, Y C1 may include -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'-, or -SO2NR'-. C1 The inclusion of these groups can improve liquid repellency.

[0365] ○ Y C2 YC2 This is a linker of an optionally substituted hydrocarbon, an optionally substituted hydrocarbon aromatic ring, or an optionally substituted heterocycle.

[0366] Y C2 Y may be a hydrocarbon group or a non-hydrocarbon group (including heteroatoms). C2 Y may be aliphatic or aromatic. C2 The chain may be linear, branched, or annular.

[0367] Y C2 Y is a group with two or more valent values. C2 The valence may be, for example, 2-4, 2-3, or 2.

[0368] Y C2 The number of carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, and may also 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.

[0369] Y C2 It consists of one or more selected from the group consisting of a di- to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have substituents, a di- to tetravalent hydrocarbon aromatic ring which may have substituents, and a di- to tetravalent heterocycle which may have substituents.

[0370] A divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or linear hydrocarbon group. A 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 in a divalent 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, and may also be 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less. The valency 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.

[0371] Aliphatic hydrocarbon groups may have substituents. Examples of substituents include -OR', -N(R')2, -COOR', and halogen atoms (wherein 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 in each occurrence). Substituents may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In a substituted aliphatic hydrocarbon group, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0372] Examples of divalent to tetravalent hydrocarbon aromatic rings include groups obtained by removing 2 to 4 hydrogen atoms from hydrocarbon aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthacene), pentacene, pyrene, and coronene. The number of ring constituent atoms of the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valency of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0373] The hydrocarbon aromatic ring may have substituents. Examples of substituents include -R', -OR', -N(R')2, -COOR', and halogen atoms (wherein 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 in each occurrence). The substituents may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the 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, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0374] The 2-4 valent heterocycle may be an aliphatic group or an aromatic group. Examples of 2-4 valent heterocycles include groups obtained by removing 2-4 hydrogen atoms from pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, etc. The number of ring constituent atoms of the heterocycle is 3-20, 4-16, or 5-12, preferably 5-12. The valency of the heterocycle may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0375] The heterocycle may have substituents. Examples of substituents include -R', -OR', -N(R')2, -COOR', and halogen atoms (wherein 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 in each occurrence). The substituents may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In a substituted heterocycle, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, for example, 65 mol% or more, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less.

[0376] Y C2 Examples include, -Ali- -Cy- -Ali(-)2 -Cy(-)2 (-)2Ali- (-)2Cy- (-)2Ali(-)2 (-)2Cy(-)2 -Ali-Cy- -Cy-Ali- -Cy-Ali-Cy- -Ali-Cy-Ali- [In the formula, Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and Cy is a hydrocarbon aromatic ring or heterocycle.] These are some examples.

[0377] Y C2 Specific examples include: -(CH2) p -(p is 1-40, 1-20, or 1-10), A linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and unsaturated bonds. 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 between 0 and 20, for example between 1 and 10, and Cy is a hydrocarbon aromatic ring or heterocycle) These are some examples.

[0378] (Y C Example) Y C Let's explain an example. In the following, R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms) in each instance.

[0379] Y C An example is Y C If it 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 - are some examples.

[0380] Y C An example is Y C If it 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 -YC1 -)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 [[ID=4\1]](-)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 -)2 etc. can be mentioned.

[0381] Y C As an example of Y C when it is tetravalent, -Y C1 (-)3, -Y C1 -Y C2 (-)3, -Y C1 -(YC2 -), 3, -Y C1 -Y C2 -Y C1 (-), 3, -Y C1 -Y C2 (-Y C1 -), 3, -Y C1 -(Y C2 -Y C1 -), 3, -Y C1 -Y C2 -Y C1 -Y C2 (-), 3, -Y C1 -Y C2 -Y C1 -(Y C2 -), 3、 -Y C1 -Y C2 -(Y C1 -Y C2 -), 3、 -Y C1 -(Y C2 -Y C1 -Y C2 -), 3; -Y C2 (-), 3, -Y C2 -Y C1 (-), 3, -Y C2 -(Y C1 (-), 3, -Y C2 -Y C1 -Y C2 (-), 3, -Y C2 -Y C1 (-Y C2 (-), 3, -Y C2 -(Y C1 -Y C2 (-), 3, -Y C2 -Y C1 -Y C2 -Y C1 (-), 3, -Y C2 -Y C1 -Y C2 -(Y C1 -), 3、 -Y C2 -Y C1 -(Y C2 -Y C1 -), 3、 -Y C2 -(Y C1 -Y C2 -Y C1 -), 3; etc. can be mentioned.

[0382] Y C A preferred example of this is -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, These are some examples.

[0383] (Preferred Y C Example) Preferably, Y C but -Y C11 -, or -Y C11 -Y C21 -Y C12 - [In the formula, each symbol is independent in each occurrence.] Y C11 However, it is -O- or -NR'-, Y C21 However, it is a hydrocarbon group with 1 to 40 carbon atoms. Y C12 is -O-, -OC(=O)-, -OC(=O)-O-, -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO2-, -SO2NR'-, -C(OR')R'-, or -C(OR')(-)2. That's fine.

[0384] Y C11 It is a non-hydrocarbon linker, and is either directly bonded or a divalent or more valent group.

[0385] Y C11 The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and may also be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0386] Y C11 The bond may be a direct bond, -C(=O)-, -C(=O)-NR'-, or -C(=S)-NR'-.

[0387] Y C21 This is a linker of a divalent hydrocarbon, which may be a hydrocarbon group having 1 to 40 carbon atoms.

[0388] Y C21 The number of carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, and may also 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.

[0389] Here, the hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or straight hydrocarbon group, and may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group.

[0390] Y C21 Specific examples include: -(CH2) p -(p is 1-40, 1-20, or 1-10), A linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and unsaturated bonds. 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 between 0 and 20, for example between 1 and 10, and Cy is a hydrocarbon aromatic ring or heterocycle) These are some examples.

[0391] Y C12may be -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO2-, -SO2NR'-, -C(OR')R'-, or -C(OR')(-)2.

[0392] Y C12 It 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 sulfonurea group, a sulfonurethane group, or a sulfonimide group. For example, Y C12 It may be -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'-, or -SO2NR'-. C12 The inclusion of these groups can improve liquid repellency.

[0393] (Z C ) Z C This is a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have substituents, or a monovalent polysiloxane group, and the above-mentioned explanations of (hydrocarbon groups having 6 or more carbon atoms, which may have substituents) and (polysiloxane groups) are used.

[0394] [Other modifying groups] The hydroxyl group of the polycarboxylic acid is -Y C -Z C n It may be substituted with other modifying groups. Examples of modifying groups are anionic groups and / or cationic groups. For anionic groups and / or cationic groups, refer to the explanation of [other modifying groups] in polyols above.

[0395] [Manufacturing method] Polycarboxylic acid modified compounds may also be produced by reacting a modifying agent having a modifying group (or a precursor structure of a modifying group) with the hydroxyl group of a polycarboxylic acid.

[0396] (Polycarboxylic acid) Polycarboxylic acids are compounds having two or more carboxyl groups and are used as raw materials for polycarboxylic acid-modified compounds. A polycarboxylic acid is a compound having two or more carboxyl groups in its molecule. Polycarboxylic acids may be aliphatic or aromatic, but are preferably aliphatic.

[0397] Polycarboxylic acids may be low molecular weight (e.g., weight-average molecular weight less than 1000, 500 or less) and / or high molecular weight. The weight-average molecular weight of a 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, 300000 or more, or 500000 or more, and may also be 1000000 or less, 7500000 or less, 500000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 10000 or less, 5000 or less, 30000 or less, 2000 or less, 1000 or less, or 500 or less.

[0398] The number of carboxyl groups in a polycarboxylic acid may be 2 or more, 5 or more, 7 or more, 10 or more, 15 or more, 30 or more, 50 or more, or 100 or more, and may also 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.

[0399] The carboxyl group equivalent of a polycarboxylic acid may be 20 or more, 40 or more, 60 or more, 80 or more, 100 or more, 120 or more, or 150 or more, and may also 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 a polycarboxylic acid is the value obtained by dividing the weight-average molecular weight of the polycarboxylic acid by the number of hydroxyl groups.

[0400] Polycarboxylic acids may be natural products. These natural products may be high molecular weight natural products, low molecular weight natural products, or derivatives thereof. The natural products may also include compounds converted from microorganisms.

[0401] 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.

[0402] Dicarboxylic acids are compounds having two carboxyl groups, and examples include oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, phthalic acid, terephthalic acid, malic acid, tartaric acid, aldaric acid, and salts thereof.

[0403] Tricarboxylic acids are compounds having three carboxyl groups, and examples include citric acid, tricarbaryl acid, t-aconitic acid, trimetic acid, and their salts.

[0404] Tetracarboxylic acids are compounds having four carboxyl groups, such as pyromellitic acid and its salts.

[0405] Carboxyl group-containing compound polymers are compounds having five or more carboxyl groups, and examples 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.

[0406] (Modifier) The modifier is preferably a compound that is reactive with polycarboxylic acid and has a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have substituents, or a monovalent polysiloxane group, as described above.

[0407] Examples of modifiers are as follows: Epoxy (CH2OCH)CH2O-Z C Amine H2N-Z C Hydroxy HO-ZC [In the formula, Z C This is as stated above.

[0408] Z in the structure of the modifier described above C This can be replaced with any group that constitutes the modifying group, for example, Z C This may be a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have substituents, or for example, Z C to -Y C -Z C n That is also acceptable.

[0409] Polycarboxylic acid modifiers may also be synthesized by reacting a polycarboxylic acid with a modifying agent. For example, a polycarboxylic acid modifier can be produced by reacting an epoxy compound modifying agent with the carboxyl group of a polycarboxylic acid to form an ester bond. The reaction conditions between the polycarboxylic acid and the modifying agent can be appropriately designed by those skilled in the art, depending on the desired product, by using a catalyst (e.g., an acid catalyst or a base catalyst), a condensing agent, etc.

[0410] 〔wax〕 As an example of a liquid-repellent compound, wax will be described. The liquid-repellent agents of this disclosure may include wax, particularly hydrocarbon wax. The wax may be an organic substance that is solid at room temperature and becomes liquid when heated. For example, the wax may be a hydrocarbon compound or a compound having a hydrocarbon group (e.g., alkyl group) with 6 to 40 carbon atoms.

[0411] The wax in this disclosure adheres to a substrate (particularly a pulp substrate) and can impart to the substrate liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or stain resistance.

[0412] [Wax properties, etc.] The properties of the wax are shown below.

[0413] The wax may be in particulate form (powder). The average particle size of the wax may be 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.2 μm or more, 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, or 0.6 μm or more, and may also be 10 μm or less, 5 μm or less, 3 μm or less, 1 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, 0.3 μm or less, or 0.2 μm or less, preferably 1 μm or less. The above particle sizes are primary particle sizes. Being within the above range can result in excellent particle stability and good liquid repellency. The average particle size can be measured with a microscope (scanning electron microscope). Specifically, a sample of wax particles is observed with a microscope at any magnification. Next, if the particle shape is spherical, its diameter will be considered as the particle size; if it is non-spherical, the average of the longest and shortest diameters will be considered as the particle size. The particle size of all particles present in the field of view will be measured, and the field of view will be moved and the particle size measured again. By repeating this process, the particle size will be measured at more than 100 points, and the average value of these measurements will be taken as the average particle size.

[0414] The HD (n-hexadecane) contact angle of the wax may be 10° or more, 20° or more, 25° or more, 30° or more, 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 60° or more, or 65° or more, preferably 25° or more, more preferably 30° or more, and may also be 100° or less, 90° or less, or 75° or less. By having an HD contact angle of the wax above the lower limit, good liquid repellency (especially oil repellency) can be imparted to the substrate. The HD contact angle is the static contact angle of the wax with respect to the spin-coated film, and is obtained by dropping 2 μL of HD onto the spin-coated film and measuring the contact angle 1 second after dropping.

[0415] The water contact angle of the wax may be 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 65° or more, 75° or more, 85° or more, 90° or more, or 100° or more, and may also 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 wax above the lower limit, good liquid repellency (especially water repellency) can be imparted to the substrate. The water contact angle is the static contact angle of the wax 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.

[0416] The wax may be low molecular weight (for example, molecular weight of 1000 or less, or 500 or less) or high molecular weight. If the wax is high molecular weight, its weight-average molecular weight may be 1000 or more, 3000 or more, 5000 or more, 7500 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more, and may also be 10000000 or less, 7500000 or less, 5000000 or less, 3000000 or less, 1000000 or less, 750000 or less, 500000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 100000 or less, 7500 or less, 5000 or less, or 3000 or less.

[0417] The melting point of the wax may be 30°C or higher, 40°C or higher, 50°C or higher, 60°C or higher, 80°C or higher, 100°C or higher, or 120°C or higher, preferably 40°C or higher, particularly preferably 55°C or higher, and may also be 250°C or lower, 225°C or lower, 200°C or lower, 150°C or lower, 130°C or lower, 120°C or lower, 110°C or lower, 100°C or lower, 80°C or lower, or 50°C or lower, preferably 120°C or lower. The melting point of the wax may be measured in accordance with JIS K 2235-1991. The melting point usually corresponds to the peak top temperature of the endothermic peak of the maximum temperature before melting observed in DSC (Differential Scanning Calorimetry).

[0418] [Types of wax, etc.] Examples of waxes include mineral waxes (petroleum waxes) such as paraffin wax, microcrystalline wax, montane wax, ozokerite wax, ceresin wax, and petrolatum wax; and synthetic waxes such as Fischer-Tropsch wax, polyethylene wax, and polypropylene wax, with paraffin wax or microcrystalline wax being preferred. The wax in this disclosure may be a hydrocarbon wax, preferably a linear aliphatic hydrocarbon, for example, a linear or branched hydrocarbon, and particularly a linear hydrocarbon.

[0419] [Isocyanate derivatives] As an example of a liquid-repellent compound, isocyanate derivatives will be described. In this disclosure, isocyanate derivatives may be used as water-repellent compounds. The isocyanate derivative has a hydrocarbon group having 6 to 40 carbon atoms, in particular a monovalent hydrocarbon group having 6 to 40 carbon atoms.

[0420] Isocyanate derivatives are compounds obtained by the reaction of an active hydrogen compound with a starting isocyanate, and have a portion derived from the active hydrogen-containing compound and a portion derived from the starting isocyanate. Unlike isocyanate-based curing agents, isocyanate derivatives do not usually have an isocyanate group.

[0421] Isocyanate derivatives have an -NHCO- group formed by the reaction of an active hydrogen compound with a starting isocyanate (where -NHCO- may be part of a urethane group or urea group). The -NHCO- group is formed by the reaction of an active hydrogen-containing group (typically a hydroxyl group) of the active hydrogen compound with an active hydrogen-reactive group (typically an isocyanate group) of the starting isocyanate. Isocyanate derivatives are typically urethanes (especially polyurethanes).

[0422] The hydrocarbon group having 6 to 40 carbon atoms in the isocyanate derivative is preferably a monovalent hydrocarbon group. For hydrocarbon groups having 6 to 40 carbon atoms, refer to the above explanation (of hydrocarbon groups having 6 or more carbon atoms that may have substituents).

[0423] The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be branched, cyclic, or linear, more preferably linear, particularly linear. The number of carbon atoms in the hydrocarbon group may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, preferably 10 or more, 12 or more, or 16 or more, and may also 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.

[0424] The weight-average molecular weight of the isocyanate derivative may be 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more, and may also 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, or 5000 or less.

[0425] [Active hydrogen compounds] Active hydrogen compounds contain active hydrogen groups that react with isocyanate groups.

[0426] Examples of active hydrogen groups include hydroxyl groups, amino groups, and carboxyl groups, but typically it is the hydroxyl group.

[0427] (α1) hydrocarbon alcohol The active hydrogen compound may be an active hydrogen compound (α1) composed of a hydrocarbon group and a hydroxyl group.

[0428] The hydrocarbon group in the active hydrogen compound (α1) is a hydrocarbon group having 6 to 40 carbon atoms as described above, and the above explanation applies accordingly.

[0429] Furthermore, the active hydrogen compound (α1) preferably has one hydroxyl group per molecule.

[0430] Examples of active hydrogen compounds (α1) include linear saturated hydrocarbon group-containing alcohols such as n-tridecanol, n-tetradecanol, n-pentadecanol, n-hexadecanol, n-heptadecanol, n-octadecanol (stearyl alcohol), n-nonadecanol, and eicosanol; branched saturated hydrocarbon group-containing alcohols such as isomiristyl alcohol, isocetyl alcohol, isostearyl alcohol, and isoicosyl alcohol; linear unsaturated hydrocarbon group-containing alcohols such as tetradecenyl alcohol, hexadecenyl alcohol, oleyl alcohol, icocenyl alcohol, dococenyl alcohol, tetracocenyl alcohol, hexacocenyl alcohol, and octacocenyl alcohol; and branched unsaturated hydrocarbon group-containing active hydrogen compounds such as phytol.

[0431] Here, a linear saturated hydrocarbon group-containing alcohol and a linear unsaturated hydrocarbon group-containing alcohol may be used in combination. When a linear saturated hydrocarbon group-containing alcohol and a linear unsaturated hydrocarbon group-containing alcohol are used in combination, the blending ratio of the linear saturated hydrocarbon group-containing alcohol is, for example, 40 parts by mass or more, preferably 55 parts by mass or more, more preferably 70 parts by mass or more, and also, for example, 90 parts by mass or less, preferably 80 parts by mass or less, based on 100 parts by mass of the total amount of the linear saturated hydrocarbon group-containing alcohol and the linear unsaturated hydrocarbon group-containing alcohol. The blending ratio of the linear unsaturated hydrocarbon group-containing alcohol is, for example, 10 parts by mass or more, preferably 20 parts by mass or more, and also, for example, 60 parts by mass or less, preferably 45 parts by mass or less, and more preferably 30 parts by mass or less, based on 100 parts by mass of the total amount of the linear saturated hydrocarbon group-containing alcohol and the linear unsaturated hydrocarbon group-containing alcohol. If the proportion of linear saturated hydrocarbon group-containing alcohol is above the lower limit mentioned above, the crystallinity of the hydrocarbon group will improve, and as a result, the liquid repellency of the treated material treated with this repellent may be improved.

[0432] (α2) Sugar alcohol / hydroxy acid modified compound The active hydrogen compound may be a sugar alcohol / hydroxy acid modified product (α2), which is a sugar alcohol / hydroxy acid (sugar alcohol and / or hydroxy acid) modified with a hydrocarbon group having 6 to 40 carbon atoms. The type of sugar alcohol / hydroxy acid is not limited and may be cyclic or acyclic. Examples of sugar alcohols include monosaccharides, reducing sugars, amino sugars, aldonic acids, and aldonic acid lactones, while examples of hydroxy acids include hydroxypolycarboxylic acids. The sugar alcohol / hydroxy acid may be a substance that exists in living organisms. Examples of sugar alcohols / hydroxy acids include compounds derived from aldoses and ketoses, such as tetrose, pentose, hexose, and heptose, but are not limited to these. Specific examples include glucose, glyceraldehyde, erythrose, arabinose, ribose, arabinose, allose, altrose, mannose, xylose, lyxose, glycerol, galactose, talose, fructose, ribulose, mannoheptulose, sedoheptulose, threose, erythritol, threitol, glucopyranose, and mannopyranose. Examples include sugar alcohols, taropyranose, allopyranose, altropyranose, idopyranose, globyranose, glucitol, mannitol, erythritol, sorbitol, arabitol, xylitol, ribitol, galactitol, fusitol, iditol, inositol, pentaerythritol, dipentaerythritol, boremitol, gluconic acid, glyceric acid, xylonic acid, galactaric acid, ascorbic acid, citric acid, gluconate lactone, glyceric acid lactone, xylonate lactone, glucosamine, galactosamine, or mixtures thereof. The number of carbon atoms in the sugar alcohol / hydroxy acid may be 2 or more, 4 or more, or 6 or more, and may be 30 or less, 20 or less, or 10 or less. The average OH value of the compound (α2) may be in the range of greater than 0 to about 230, preferably about 10 to about 175, most preferably about 25 to about 140.

[0433] The number of hydrocarbon groups having 6 to 40 carbon atoms in the sugar alcohol / hydroxy acid modified product (α2) may be 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more, and may also be 12 or less, 9 or less, 6 or less, or 3 or less.

[0434] In the sugar alcohol / hydroxy acid modified product (α2), at least one active hydrogen (e.g., hydrogen in the OH group, carboxyl group) of the sugar alcohol and / or hydroxy acid is -R α2 , -C(O)R α2 -(CH2CH2O) n (CH(CH3)CH2O) m R α2 -(CH2CH2O) n (CH(CH3)CH2O) m C(O)R α2 R may be substituted with an active hydrogen substituent selected from a mixture thereof. α2 is a hydrogen atom or a hydrocarbon group having 6 to 40 carbon atoms, where each n is independently 0 to 20, each m is independently 0 to 20, and m+n may be greater than 0. Compound (α2) has at least one active hydrogen, and for example, in a sugar alcohol / hydroxy acid modified product, at least one (1 or more) of the active hydrogens of the sugar alcohol / hydroxy acid may be unmodified, and this active hydrogen (e.g., an -OH group) may react with the active hydrogen reactant group (especially an isocyanate group) of compound (b) to form -NHCO-.

[0435] (α21) sorbitan modified compound The sugar alcohol / hydroxy acid modified product (α2) may be a sorbitan modified product (α21) obtained by modifying sorbitan with a hydrocarbon group having 6 to 40 carbon atoms, and may particularly be an alkylsorbitan, with sorbitan being -R α2 , -C(O)R α2 -(CH2CH2O) n (CH(CH3)CH2O) m R α2 -(CH2CH2O) n (CH(CH3)CH2O) m C(O)R α2, or compounds substituted with a mixture thereof (where R α2 (A hydrocarbon group has 6 to 40 carbon atoms). For example, sorbitan is -C(O)R α2 The compound may be monosubstituted, disubstituted, or trisubstituted. Here, sorbitan may contain amounts of sorbitol, isosorbide, or other intermediates or by-products. Commercially available sorbitan such as SPAN can be used as the alkylsorbitan.

[0436] In one embodiment, at least one active hydrogen substituent is -C(O)R α2 It is fine if R α2 The C1 is a linear or branched alkyl group having 6 to 40 carbon atoms, more preferably 7 to 21, and most preferably 11 to 21 carbon atoms. Preferred compounds include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, and monosubstituted, disubstituted, and trisubstituted sorbitans derived from mixtures thereof. Particularly preferred compounds include monosubstituted, disubstituted, and trisubstituted sorbitan stearates, or sorbitan behenin.

[0437] In one embodiment, R α2 It may contain at least one unsaturated bond. An example of such a compound (at least one active hydrogen substituent is -C(O)R α2 Selected from, R α2 As an example of a compound containing at least one unsaturated bond, sorbitan trioleate (i.e., in the formula, R α2 -C7H 14 CH=CHC8H 17 Examples include, but are not limited to, palmitoleic acid, linoleic acid, arachidonic acid, and erucic acid, which are monosubstituted, disubstituted, and trisubstituted sorbitans.

[0438] In one embodiment, the sorbitan modified product (α21) has at least one active hydrogen substituent, and the active hydrogen substituent is independently -(CH2CH2O)n (CH(CH3)CH2O) m R α2 or -(CH2CH2O) n (CH(CH3)CH2O) m C(O)R α2 (where m is independently between 0 and 20, and n is independently between 0 and 20, and m+n is greater than 0). Such compounds are known as polysorbates and are marketed under the trademark name TWEEN. These sorbitans are R α2 Therefore, monosubstituted, disubstituted, or trisubstituted compounds can be used. Commercially available polysorbates have each R 2 From various polysorbates where H is unsubstituted, each R α2 It is known to contain a wide range of mixtures, from polysorbates in which the linear or branched alkyl group has 6 to 40 carbon atoms (fully substituted), to mixtures of various substitutions thereof. Examples of such sorbitan modified products (α21) include polysorbates such as polysorbate tristearate and polysorbate monostearate. m+n is greater than 0, and R α2 Examples of sorbitan modifications (α21) containing at least one unsaturated bond include, but are not limited to, polysorbate trioleates (where R α2 C7H 14 CH=CHC8H 17 Examples include (which are commercially available under the name polysorbate 80). The sorbitan modified product (α21) may contain a mixture of compounds having various active hydrogen substituents, and R α2 A compound containing at least one unsaturated bond, and R α2 It may also contain a mixture with a completely saturated compound.

[0439] (α22) Citrate modified compound The sugar alcohol / hydroxy acid modified product (α2) may be a citrate modified product (α22) obtained by modifying citrate with a hydrocarbon group having 6 to 40 carbon atoms, and may particularly be an alkyl citrate. For example, the citrate modified product (α22) may exist as a monosubstituted, disubstituted, or trisubstituted product having an alkyl group. A mixture of citrates having active hydrogen substituents of various values ​​may be used, and R α2 A compound having a hydrocarbon group having at least one unsaturated bond, and R α2 It may also contain a mixture with a compound that is a completely saturated hydrocarbon. The citrate-modified compound (α22) is -(CH2CH2O) n (CH(CH3)CH2O) m R α2 Alternatively, -(CH2CH2O) n (CH(CH3)CH2O) m C(O)R α2 It may have an active hydrogen substituent selected from (where R α2 (This refers to a hydrocarbon group having 6 to 40 carbon atoms). Examples of citrate-modified (α22) compounds include, but are not limited to, trialkyl citrates.

[0440] (α23) Pentaerythritol Modified Form The sugar alcohol / hydroxy acid modified product (α21) may be a pentaerythritol modified product (α23) obtained by modifying pentaerythritol with a hydrocarbon group having 6 to 40 carbon atoms, and may be a monosubstituted, disubstituted, or trisubstituted product having a hydrocarbon group (especially an alkyl group) having 6 to 40 carbon atoms, for example, a dipentaerythriol ester. The active hydrogen substituent is -CH2C[CH2OR α2 ]3 may be included (where R α2 ( is a hydrocarbon group with 6 to 40 carbon atoms). Also, pentaerythritol modified compounds (α23) are compounds having a mixture of hydrocarbon groups with different chain lengths, or R α2 A compound containing at least one unsaturated bond, and R α2 It may also contain a mixture with a completely saturated compound.

[0441] (α3) Cationic Active Hydrogen Compounds The active hydrogen compound may be a cationic active hydrogen compound (α3) having an active hydrogen group and a cationic group.

[0442] Furthermore, the cationic active hydrogen compound (α3) preferably has two or more hydroxyl groups per molecule.

[0443] Examples of cationic groups include tertiary amino groups.

[0444] In other words, the cationic active hydrogen compound (α3) preferably has two or more hydroxyl groups per molecule as active hydrogen groups and a tertiary amino group as a cationic group.

[0445] Such cationic active hydrogen compounds can impart good dispersibility to liquid media (e.g., water), and can also introduce cationic groups that have affinity for textile products (described later) into the resin, thereby improving wash durability.

[0446] More preferably, the cationic active hydrogen compound has two hydroxyl groups per molecule as active hydrogen groups and a tertiary amino group as a cationic group.

[0447] Examples of such cationic active hydrogen compounds include alkyldialkanolamines such as N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, N-methyldipropanolamine, and propanolamine, as well as trialkanolamines such as N-triethanolamine and N-triisopropanolamine, with N-methyldiethanolamine being preferred.

[0448] The cationic active hydrogen compound (or the portion of the hydrophobic compound derived from the cationic active hydrogen compound) may form a salt with the acid compound.

[0449] Examples of acid compounds include organic acids and inorganic acids. Examples of organic acids include acetic acid, lactic acid, tartaric acid, and malic acid, with acetic acid and lactic acid being preferred, and acetic acid being more preferred. Examples of inorganic acids include hydrochloric acid, sulfuric acid, and phosphoric acid, with hydrochloric acid being preferred. Examples of acid compounds include organic acids. If the acid compound contains an organic acid, the acid will volatilize upon heat treatment, thereby improving the liquid repellency of the treated material. Furthermore, the volatilization of the acid upon heat treatment can improve the wash durability of textile products, as the cationic groups are more easily adsorbed onto the textile products. (α4) Other active hydrogen-containing compounds The active hydrogen compound (α) may also contain other active hydrogen compounds (α4).

[0450] (α41) Compound The active hydrogen compound (α4) is, R α41 -X α41 [In the formula, In the formula, R α41 teeth, C1-C may contain at least one unsaturated group. 30 Linear or branched alkyl, hydroxy-functional C1-C 30 Linear or branched alkyl, hydroxy-functional linear or branched C1-C 30 Polyethers, hydroxy-functional linear or branched polyesters, hydroxy-functional linear or branched organosiloxanes, thiol-functional C1-C 30 Linear or branched alkyl, amine-functionalized C1-C 30 Linear or branched alkyl, Y - R α411 R α412 R α413 N + -R α414 -(Here, Y is a halide ion, for example, Cl - It is. ), HOS(=O)2-R α414 -, or R α411 R α412 C = N - (where R α411 , R α412 , Rα413 Each of them is independently -H and C1-C6 alkyl, and R α414 It is a divalent alkyl group having 1 to 20 carbon atoms. X α41 is -OH, -C(O)OH, -SH, -NH(R'), -O-(CH2CH2O) s (CH(CH3)CH2O) t -H or -C(O)-O-(CH2CH2O) s (CH(CH3)CH2O) t -H is an isocyanate-reactive functional group (where R ’ is a -H or monovalent organic group, s is an integer between 0 and 50, t is an integer between 0 and 50, and s+t is greater than 0. The compound may be represented by (α41).

[0451] Compound (α41) may be a hydrophilic, water-soluble material containing at least one hydroxy-terminated polyether, where X α41 is -O-(CH2CH2O) s (CH(CH3)CH2O) t -H or -C(O)-O-(CH2CH2O)s(CH(CH3)CH2O) t -H. -(CH2CH2O)- represents an oxyethylene group (EO), and -(CH(CH3)CH2O)- represents an oxypropylene group (PO). These polyethers may contain only EO groups, only PO groups, or mixtures thereof. These polyethers may also exist as the specified PEG-PPG-PEG (polyethylene glycol-polypropylene glycol-polyethylene glycol) triblock copolymer.

[0452] In one embodiment, X α41 -OH, -C(O)OH, -SH, -NH(R ’ ) and R α41 C1-C12 contains at least one unsaturated group, which can be selected as optional. 30 Linear or branched alkyl, hydroxy-functional C1-C 30Linear or branched alkyl, hydroxy-functional linear or branched C1-C 30 Polyethers, hydroxy-functional linear or branched polyesters, hydroxy or amine-functional linear or branched organosiloxanes, thiol-functional C1-C 30 Linear or branched alkyl, amine-functionalized C1-C 30 Selected from linear or branched alkyl groups.

[0453] X α41 (R) may be an -OH group, and examples of such compounds (α41) include alkyl alcohols such as propanol and butanol, or aliphatic alcohols including stearyl alcohol. α41 It optionally contains at least one unsaturated group, C1-C 30 Alkyl diols or polyols (R) such as linear or branched alkyls, ethanediol, propanediol, butanediol, or hexanediol. α41 These are hydroxy-functional C1-C 30 Alkylene glycol ethers such as linear or branched alkyl triethylene glycol, tetraethylene glycol, poly(ethylene glycol) (PEG), poly(propylene glycol) (PPG), poly(tetrahydrofuran), or glycol ethers having a mixture of PEG, PPG, or THF units (R α41 These are hydroxy-functional linear or branched C1-C chains. 30 Polyether, polyester polyol (R α41 (These are hydroxy-functional linear or branched polyesters), silicone prepolymer polyols (R α41 (These are hydroxy-functional linear or branched organosiloxanes), N,N-dimethylaminoethanol (R α41 This is amine functional C1~C 30 (Straight-chain or branched-chain alkyl), choline chloride or betaine HCl (R α41 Y - R α411 R α412 R α413 N + -R α414-is), butanone oxime (R α41 R α411 R α412 Examples include, but are not limited to, polyether polyols (where C=N-). Polyether polyols may contain only EO groups, only PO groups, only THF groups, or mixtures thereof. These polyethers may also exist as block copolymers, such as those specified by PEG-PPG-PEG (polyethylene glycol-polypropylene glycol-polyethylene glycol). Polyether glycols preferably have an average molecular weight of about 200 or more, most preferably 350 to 2000.

[0454] X α41 This may be -C(O)OH, and examples of such compounds (α41) include fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, palmitoleic acid, linoleic acid, arachidonic acid, oleic acid, or erucic acid (R α41 C1-C12 contains at least one unsaturated group, which can be selected as optional. 30 Hydroxy-containing acids (R) such as linear or branched alkyl, hydroxycaprylic acid, hydroxycapric acid, hydroxylauric acid, hydroxymyristic acid, hydroxypalmitic acid, hydroxystearic acid, hydroxyarachidic acid, hydroxybehenic acid, hydroxylignoceric acid, hydroxypalmitoleic acid, hydroxylinoleic acid, hydroxyarachidonic acid, hydroxyoleic acid, or hydroxyerucic acid. α41 These are hydroxy-functional C1-C 30 (Linear or branched alkyl), and mercaptoalkanoic acids such as mercaptopropionic acid (R α41 This is thiol functionality C1~C 30 Examples include, but are not limited to, linear or branched alkyl groups.

[0455] X α41 This may be -SH, and examples of such compounds (α41) include alkylthiols such as lauryl mercaptan or dodecyl mercaptan (Rα41 C1-C12 contains at least one unsaturated group, which can be selected as optional. 30 Examples include, but are not limited to, linear or branched alkyl groups.

[0456] X α41 This may be -NH(R'), and examples of such compounds (α41) include alkylamines such as diisopropylamine, propylamine, hexylamine, or laurylamine (R α41 C1-C12 contains at least one unsaturated group, which can be selected as optional. 30 Alkanolamines such as linear or branched alkyl groups, ethanolamine, or propanolamine (R α41 These are hydroxy-functional C1-C 30 (Linear or branched alkyl), silicone prepolymer polyamine (R α41 (These are amine-functional linear or branched organosiloxanes), alkyldiamines (R α41 This is amine functional C1~C 30 (R) are linear or branched alkyl groups, and aminoalkanesulfonic acids such as 2-aminoethanesulfonic acid. α41 HO-S(O)2R α414 - is one example, but is not limited to these.

[0457] (α42) compound Compound (α42) is, R α421 -(OCH2CH(OR α422 )CH2) z -OR α423 [In the formula, R α421 , R α422 and R α423 is at least one R α421 , R α422 or R α423 -H is -H, and independently of each other, -H and -R α424 , -C(O)R α424 And R α424This is a linear or branched alkyl group having 5 to 29 carbon atoms, which may independently contain at least one unsaturated bond, and z is 1 to 15.

[0458] Compound (α42) may be any compound commonly known as polyglycerol. Other specific examples include, but are not limited to, triglycerol monostearate, triglycerol distearate, hexaglycerol monostearate, hexaglycerol distearate, decaglyceryl mono(caprylate / capate), decaglyceryl di(caprylate / capate), decaglycerol, polyglycerol-3, and C18 diglycerides.

[0459] (α43) chain extender Compound (α4) may also be a chain extender (α43). The chain extender (α43) is a compound having two or more (for example, two) functional groups containing active hydrogen within its molecule. Known chain extenders can be used as chain extenders, and examples include aliphatic or aromatic diols or polyols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripylene glycol, 1,4-butanediol, 1,6-hexanediol, and cyclohexanedimethanol; aliphatic or aromatic diamines or polyamines such as ethylenediamine, piperazine, aminoethylpiperazine, phenylenediamine, and diethyltoluenediamine; phenol hydroxyl group-containing compounds such as resorcinol, catechol, hydroquinone, bisphenol, bisphenol A, bisphenol AP (1,1-bis(4-hydroxylphenyl)-1-phenylethane), bisphenol F, bisphenol K, bisphenol M, tetramethylbiphenol, and o,o'-diallyl-bisphenol A; and alcohol amines such as aminoethylethanolamine, aminopropylethanolamine, aminohexylethanolamine, aminoethylpropanolamine, aminopropylpropanolamine, and aminohexylpropanolamine.

[0460] [Raw material isocyanate] The fluorine-containing compound has a portion derived from the raw material isocyanate.

[0461] Examples of raw material isocyanates include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or mixture thereof) (TDI), phenylene diisocyanate (m-,p-phenylene diisocyanate or mixture thereof, 4,4'-diphenyl diisocyanate, diphenylmethane diisocyanate (4,4'-, 2,4' or 2,2'-diphenylmethane diisocyanate or mixture thereof) (MDI), 4,4'-toluidine isocyanate (TODI), 4,4'-diphenyl ether diisocyanate, xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or mixture thereof) (XDI), tetramethylxylylene diisocyanate (1,3- or Aromatic polyisocyanates selected from 1,4-tetramethylxylylene diisocyanate or a mixture thereof (TMXDI), ω,ω'-diisocyanate-1,4-diethylbenzene, naphthalene diisocyanate (1,5-, 1,4- or 1,8-naphthalene diisocyanate or a mixture thereof) (NDI), triphenylmethane triisocyanate, tris(isocyanatephenyl)thiophosphate, polymethylene polyphenylene polyisocyanate, nitrodiphenyl-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, and 3,3'-dimethoxydiphenyl-4,4'-diisocyanate; Acyclic aliphatic polyisocyanates selected from trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), hexamethylene diisocyanate, pentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl capeate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, trimethylhexamethylene diisocyanate, and decamethylene diisocyanate; 1,3-Cyclopentane diisocyanate, 1,3-Cyclopentene diisocyanate, Cyclohexane diisocyanate (1,4-Cyclohexane diisocyanate, 1,3-Cyclohexane diisocyanate), 3-Isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (Isophorone diisocyanate, IPDI), Methylenebis(Cyclohexyl isocyanate (4,4'-, 2,4'- or 2,2'-methylenebis(Cyclohexyl isocyanate or mixtures thereof) (Hydrogenated MDI), Methylcyclohex Cyclic alicyclic polyisocyanates selected from diisocyanates (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, bis(isocyanate-methyl)cyclohexane (1,3- or 1,4-bis(isocyanate-methyl)cyclohexane or a mixture thereof) (hydrogenated XDI), dimer acid diisocyanates, transcyclohexane 1,4-diisocyanate, hydrogenated tolylene diisocyanate (hydrogenated TDI), and hydrogenated tetramethylxylylene diisocyanate (hydrated TMXDI); Bridged cyclic alicyclic polyisocyanates selected from norbornene diisocyanate, norbornene diisocyanate methyl, bicycloheptane triisocyanate, diisocyanate methyl bicycloheptane, and di(diisocyanate methyl)tricyclodecane; TIFF0007832566000022.tif15584 Compounds selected from TIFF0007832566000023.tif209118; and the above isocyanates, biuret-modified polyisocyanates, polymers of polyisocyanates (e.g., dimers, trimers (e.g., isocyanurate derivatives, iminooxadiazinedione derivatives), pentamers, heptamers, etc.), allophanate derivatives (e.g., allophanate derivatives produced by the reaction of the above polyisocyanates with monohydric or dihydric alcohols), polyol derivatives (e.g., polyol derivatives produced by the reaction of the above polyisocyanates with trihydric alcohols (e.g., trimethylolpropane, etc.) (alcohol adducts, preferably trimethylolpropane) Examples include polyisocyanate adducts, biuret derivatives (for example, biuret derivatives produced by the reaction of the above-mentioned polyisocyanate with water or amines), urea derivatives (for example, urea derivatives produced by the reaction of the above-mentioned polyisocyanate with diamines), oxadiazinetrione derivatives (for example, oxadiazinetrione produced by the reaction of the above-mentioned polyisocyanate with carbon dioxide), carbodiimide derivatives (for example, carbodiimide derivatives produced by the decarboxylation condensation reaction of the above-mentioned polyisocyanate), uretodione derivatives, uretonimine derivatives, etc.

[0462] The average number of isocyanate groups in the raw material isocyanate is 2 or more, preferably 2.5, more preferably 2.9, and also, for example, 3.8 or less. The raw material isocyanate may be a polyisocyanate having multiple isocyanate groups.

[0463] [Method for synthesizing isocyanate derivatives]

[0464] To obtain an isocyanate derivative, the active hydrogen compound and the starting isocyanate are reacted. The reaction may be carried out in one step or in multiple steps in a sequential manner. For example, if the product contains unreacted active hydrogen groups or active hydrogen reactive groups, the synthesis may be carried out sequentially. Sequential reactions are particularly useful when using substituted sugar alcohols with a high number of OH groups. The reaction conditions, such as reaction concentration and reaction temperature, are not particularly limited and can be determined by those skilled in the art. Specifically, the active hydrogen compound and the starting isocyanate may be blended such that the equivalent ratio of active hydrogen reactive groups (isocyanate groups) to active hydrogen groups (active hydrogen reactive group / active hydrogen group) is, for example, 1.2 or more, preferably 1.5 or more, and for example, 2.0 or less.

[0465] [Composition of isocyanate derivatives] The amount of the portion derived from the active hydrogen compound 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, or 70% by weight or more, relative to the isocyanate derivative, and may also be 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, or 15% by weight or less.

[0466] The amount of the portion derived from the hydrocarbon alcohol (α1) 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, or 70% by weight or more, relative to the portion derived from the active hydrogen compound, and may also be 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, or 15% by weight or less.

[0467] The amount of the portion derived from the sugar alcohol / hydroxy acid modified product (α2) may be 10% or more by weight, 20% or more by weight, 30% or more by weight, 40% or more by weight, 50% or more by weight, 60% or more by weight, or 70% or more by weight relative to the portion derived from the active hydrogen compound, and may also be 75% or less by weight, 65% or less by weight, 55% or less by weight, 45% or less by weight, 35% or less by weight, 25% or less by weight, or 15% or less by weight.

[0468] The amount of the portion derived from the cationic active hydrogen compound (α3) may be 10% or more by weight, 20% or more by weight, 30% or more by weight, 40% or more by weight, 50% or more by weight, 60% or more by weight, or 70% or more by weight relative to the portion derived from the active hydrogen compound, and may also be 75% or less by weight, 65% or less by weight, 55% or less by weight, 45% or less by weight, 35% or less by weight, 25% or less by weight, or 15% or less by weight.

[0469] The amount of the portion derived from the other active hydrogen-containing compound (α4) may be 10% or more by weight, 20% or more by weight, 30% or more by weight, 40% or more by weight, 50% or more by weight, 60% or more by weight, or 70% or more by weight relative to the portion derived from the active hydrogen compound, and may also be 75% or less by weight, 65% or less by weight, 55% or less by weight, 45% or less by weight, 35% or less by weight, 25% or less by weight, or 15% or less by weight.

[0470] The amount of the portion derived from the raw material isocyanate 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, or 70% by weight or more relative to the isocyanate derivative, and may also be 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, or 15% by weight or less.

[0471] 〔silicone〕 As an example of a liquid-repellent compound, silicone will be described. The liquid repellent in this disclosure may include silicone (polyorganosiloxane). By including silicone, in addition to the good liquid repellency derived from the polysiloxane structure, good texture and durability can be obtained.

[0472] Silicones are compounds mainly consisting of polyorganosiloxane structures, and may be unmodified silicones (such as polyalkylsiloxanes, polyalkylphenylsiloxanes, and polydimethylsiloxanes) in which reactive groups have not been modified, or modified silicones (such as amino-modified, epoxy-modified, carboxy-modified, and methylhydrogen-based silicones).

[0473] The polyorganosiloxane structure of silicone corresponds to the (polysiloxane group) described above, and we will refer to that explanation.

[0474] The silicone has a polyorganosiloxane structure as its main backbone, and the weight of SiO may be 30% or more by weight, 50% or more by weight, 70% or more by weight, or 90% or more by weight.

[0475] The silicon number of the polysiloxane group may be 3 or more, 5 or more, 6 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, and may also be 50000 or less, 25000 or less, 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, for example, 500 or less.

[0476] The silicone may be in the form of a liquid such as oil, a viscous substance, or solid particles.

[0477] [Dispersant] The repellent agent in this disclosure may include 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. In particular, the repellent agent in this disclosure may include a nonionic dispersant.

[0478] The dispersant may be either an organic dispersant or an inorganic dispersant, or a combination of both.

[0479] Organic dispersants may be used as dispersants. Organic dispersants can be classified into nonionic dispersants, anionic dispersants, cationic dispersants, and amphoteric dispersants, and the term "organic dispersant" may refer to surfactants.

[0480] The dispersant does not need to contain fluorine atoms.

[0481] [Nonionic dispersant] The dispersant may contain a nonionic dispersant. The nonionic dispersant may be a nonionic surfactant.

[0482] The nonionic dispersant may be of low molecular weight (e.g., molecular weight 2000 or less, particularly 10000 or less) or high molecular weight (e.g., molecular weight 2000 or more). The molecular weight of the nonionic dispersant may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 1000000 or less, 7500000 or less, 500000 or less, 250000 or less, 100000 or less, 50000 or less, 25000 or less, 100000 or less, 7500 or less, 5000 or less, 2500 or less, or 250 or less.

[0483] Examples of nonionic dispersants include ethers, esters, ester ethers, alkanolamides, polyols, and amine oxides.

[0484] Examples of ethers are compounds having an oxyalkylene group (preferably a polyoxyethylene group).

[0485] Examples of esters are esters of alcohols and fatty acids. Examples of alcohols are 1-30 valencies (especially 2-10 valencies) with 1-50 carbon atoms (especially 10-30 carbon atoms) (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids with 2-50 carbon atoms, especially 5-30 carbon atoms.

[0486] Examples of ester ethers are compounds formed by adding an alkylene oxide (especially ethylene oxide) to an ester of an alcohol and a fatty acid. Examples of alcohols are 1-30 valencies (especially 2-10 valencies) with 1-50 carbon atoms (especially 3-30 carbon atoms) (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids with 2-50 carbon atoms, especially 5-30 carbon atoms.

[0487] Examples of alkanolamides are formed from fatty acids and alkanolamines. Alkanolamides may be monoalkanolamides or dialkanolaminos. Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. Alkanolamines may be alkanols having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0488] The polyol may be a divalent to pentavalent alcohol with 10 to 30 carbon atoms. The amine oxide may be an oxide of an amine (a secondary amine or preferably a tertiary amine) (for example, having 5 to 50 carbon atoms).

[0489] The nonionic dispersant is preferably a nonionic dispersant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms in the alkylene group of the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic dispersant is generally preferably 2 to 100.

[0490] The nonionic dispersant is selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyols, and amine oxides, and is preferably a nonionic dispersant having an oxyalkylene group.

[0491] The nonionic dispersant may be an alkylene oxide adduct of linear and / or branched aliphatic (saturated and / or unsaturated) groups, a polyalkylene glycol ester of linear and / or branched fatty acids (saturated and / or unsaturated), a sorbitan ester of linear and / or branched fatty acids (saturated and / or unsaturated), a glycerol ester of linear and / or branched fatty acids (saturated and / or unsaturated), a polyglycerol ester of linear and / or branched fatty acids (saturated and / or unsaturated), a sucrose ester of linear and / or branched fatty acids (saturated and / or unsaturated), a polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of acetylene glycol, etc. Among these, those in which the alkylene oxide addition portion and the polyalkylene glycol portion have structures of polyoxyethylene (POE), polyoxypropylene (POP), or POE / POP copolymer (which may be random copolymer or block copolymer) are preferred. Furthermore, the nonionic dispersant does not need to contain aromatic groups.

[0492] The nonionic dispersant is, formula: R 1 O-(CH2CH2O) p -(R 2 O) q -R 3 [In the formula, R 1 This is an alkyl group having 1 to 22 carbon atoms, or an alkenyl group or acyl group having 2 to 22 carbon atoms. R 2 Each of these is independently identical or distinct, an alkylene group having 3 or more carbon atoms (e.g., 3 to 10). R 3 These are a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms. p is a number greater than or equal to 2. q is a number greater than or equal to 1, or 0. It may be a compound represented by [the formula shown].

[0493] R 1The carbon atoms have 8 to 20 carbon atoms, and are more preferably 10 to 18 carbon atoms. 1 Preferred specific examples include the octyl group, nonyl group, trimethylnonyl group, lauryl group, tridecyl group, oleyl group, and stearyl group. R 2 Examples include the propylene group and the butylene group. In nonionic dispersants, p may be a number greater than or equal to 3 (e.g., 5 to 200). q may be a number greater than or equal to 2 (e.g., 5 to 200). That is, -(R 2 O) q - may form a polyoxyalkylene chain. The nonionic dispersant may be a polyoxyethylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) in the center. Examples of hydrophobic oxyalkylene chains include oxypropylene chains, oxybutylene chains, and styrene chains, but oxypropylene chains are preferred among these.

[0494] Specific examples of nonionic dispersants include ethylene oxide and hexylphenol, isooctatylphenol, hexadecanol, oleic acid, and alkanes (C 12 -C 16 ) Thiol, sorbitan monofatty acid (C7-C 19 ) or alkyl(C 12 -C 18 This includes condensation products with amines, sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, lecithin derivatives, etc. Examples of nonionic dispersants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene polyoxybutylene alkyl ethers, polyoxyethylene polyoxypropylene glycol, polyethyleneimine ethoxylate, etc.

[0495] The proportion of polyoxyethylene blocks can be 5 to 80% by weight, for example, 30 to 75% by weight, and especially 40 to 70% by weight, relative to the molecular weight of the nonionic dispersant (copolymer). The average molecular weight of nonionic dispersants is generally 300 to 5,000, for example, 500 to 3,000. The nonionic dispersant may be a single compound or a mixture of two or more compounds. The nonionic dispersant may be a mixture of compounds with an HLB (hydrophilic-hydrophobic balance) of less than 15 (especially 5 or less) and compounds with an HLB of 15 or more. Specifically, it is preferable to select from polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene, polyoxypropylene with an HLB of 1 to 18, or from sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene glycerin fatty acid esters, and polyoxyethylene sorbitan fatty acid esters with an HLB of less than 7.

[0496] [Cationic dispersant] The dispersant may contain a cationic dispersant. The cationic dispersant may be a cationic surfactant. The cationic dispersant may be a compound that does not have an amide group.

[0497] The cationic dispersant may be of low molecular weight (e.g., molecular weight of 2000 or less, particularly 10000 or less) or high molecular weight (e.g., molecular weight of 2000 or more). The molecular weight of the cationic dispersant may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 1000000 or less, 750000 or less, 500000 or less, 250000 or less, 100000 or less, 50000 or less, 25000 or less, 100000 or less, 7500 or less, 5000 or less, 2500 or less, or 250 or less.

[0498] Cationic dispersants may be aliphatic or aromatic, such as ammonium salts (e.g., quaternary ammonium salts). Cationic dispersants may also be oxyethylene-added ammonium salts. Specifically, examples include amine salt type dispersants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazoline; quaternary ammonium salt type dispersants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzalkonium chloride, and benzethonium chloride; and polymeric cationic dispersants such as polyquaternium-1 to 47. Examples of cationic dispersants include alkylamine salts and quaternary ammonium salts.

[0499] Low molecular weight cationic dispersants are R 21 -N + (-R 22 )(-R 23 )(-R 24 )X - [In the formula, R 21 , R 22 , R 23 and R 24 is hydrogen, or a hydrocarbon group having 1 to 40 carbon atoms. X is an anionic group. It may be a compound represented by R. 21 , R 22 , R 23 and -R 24 Specific examples of X include alkyl groups (e.g., methyl group, butyl group, stearyl group, palmityl group) and aromatic groups (e.g., benzyl group, phenyl group). Specific examples of X include halogens (e.g., chlorine) and acids (e.g., hydrochloric acid, acetic acid). Examples of cationic dispersants include monoalkyltrimethylammonium salts (alkyl group with 4 to 40 carbon atoms) and benzalkonium chloride.

[0500] Specifically, low-molecular-weight cationic dispersants have the formula: R 1 p -N +R 2 q X - [In the formula, R 1 is C12 or higher (for example, C 12 ~C 50 ) is a linear and / or branched aliphatic (saturated and / or unsaturated) group, R 2 The elements are H or C1-C4 alkyl groups, benzyl groups, and polyoxyethylene groups (number of oxyethylene groups, for example, 1 (particularly 2, especially 3) to 50) (CH3 and C2H5 are particularly preferred). X is a halogen atom (e.g., chlorine), or a C1-C4 fatty acid salt, or a C1-C4 sulfonate. p is either 1 or 2, q is either 2 or 3, and p + q = 4. It may be an ammonium salt represented by R. 1 The number of carbon atoms can be 12 to 50, for example, 12 to 30.

[0501] Low molecular weight cationic dispersants 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, etc.

[0502] The polymeric cationic dispersant may be various polymers (e.g., polyquaternium-1 to 47) having cationic groups (e.g., ammonium groups, quaternary ammonium groups). Examples of polymeric cationic dispersants include cationized starch, cationized cellulose (e.g., O-(2-hydroxy-3-(trimethylammonio)propylhydroxyethylcellulose chloride), cationized guar gum, cationized xanthan gum, chitosan, and other cationized natural products (especially cationized sugars); 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 methacrylic acid, diallyldimethylammonium chloride, dimethylaminopropylamine, and quaternized vinylimidazole.

[0503] [Anionic dispersant] The dispersant may contain an anionic dispersant. The anionic dispersant may be an anionic surfactant. The dispersant does not have to contain an anionic dispersant.

[0504] The anionic dispersant may be of low molecular weight (e.g., molecular weight 2000 or less, particularly 10000 or less) or high molecular weight (e.g., molecular weight 2000 or more). The molecular weight of the anionic dispersant may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 1000000 or less, 750000 or less, 500000 or less, 250000 or less, 100000 or less, 50000 or less, 25000 or less, 100000 or less, 7500 or less, 5000 or less, 2500 or less, or 250 or less.

[0505] Examples of anionic dispersants include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkanesulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfone fatty acid salts, N-acyl amino acid type dispersants, phosphate mono or diester type dispersants, and sulfosuccinate esters. An example of anionic dispersants is a carboxylate salt (e.g., a fatty acid salt).

[0506] [Amphoteric dispersant] The dispersant may contain an amphoteric dispersant. The amphoteric dispersant may be an amphoteric surfactant.

[0507] The amphoteric dispersant may be of low molecular weight (e.g., molecular weight 2000 or less, especially 10000 or less) or high molecular weight (e.g., molecular weight 2000 or more). The molecular weight of the amphoteric dispersant may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 1000000 or less, 7500000 or less, 500000 or less, 250000 or less, 100000 or less, 50000 or less, 25000 or less, 100000 or less, 7500 or less, 5000 or less, 2500 or less, or 250 or less.

[0508] Examples of amphoteric dispersants include alanines, imidazolinium betaines, amide betaines, and betaine acetate. Specifically, these include lauryl betaine, stearyl betaine, laurylcarboxymethylhydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, and fatty acid amidopropyldimethylaminoacetic acid betaine.

[0509] [Inorganic dispersants] The dispersant may contain an inorganic dispersant.

[0510] The average primary particle size of the inorganic dispersant may be 5 nm or larger, 30 nm or larger, 100 nm or larger, 1 μm or larger, 10 μm or larger, or 25 μm or larger, and may also be 100 μm or smaller, 50 μm or smaller, 10 μm or smaller, 1 μm or smaller, 500 nm or smaller, or 300 nm or smaller. 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 also be hydrophilic particles.

[0511] Examples of inorganic dispersants include polyvalent metal phosphates such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, and hydroxyapatite; carbonates such as calcium carbonate and magnesium carbonate; silicates such as calcium metasilicate; sulfates such as calcium sulfate and barium sulfate; and hydroxides such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide.

[0512] [Amount of dispersant] The amount of dispersant may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, per 100 parts by weight of the liquid-repellent compound, or 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less.

[0513] [Liquid media] The repellent in this disclosure may include a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The repellent may be a dispersion or a solution. The repellent in this disclosure is preferably an aqueous dispersion.

[0514] Examples of organic solvents include esters (e.g., esters with 2 to 40 carbon atoms, specifically ethyl acetate and butyl acetate), ketones (e.g., ketones with 2 to 40 carbon atoms, specifically methyl ethyl ketone and diisobutyl ketone), alcohols (e.g., alcohols with 1 to 40 carbon atoms, specifically isopropyl alcohol), aromatic solvents (e.g., toluene and xylene), and petroleum solvents (e.g., alkanes with 5 to 10 carbon atoms, specifically naphtha and kerosene). The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent may contain compounds having at least one hydroxyl group (e.g., polyols such as alcohols and glycol-based solvents, ethers of polyols (e.g., monoethers)). These may be used individually or in combination of two or more.

[0515] [Amount of liquid medium] The amount of 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, or 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, per 1 part by weight of the liquid-repellent compound.

[0516] 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, or 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, per 1 part by weight of the liquid-repellent compound.

[0517] The amount of 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, or 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, per 1 part by weight of the liquid-repellent compound.

[0518] [Organic acid] The repellent agent of this disclosure may contain an organic acid. Any known organic acid can be used. Preferred organic acids include carboxylic acids, sulfonic acids, sulfinic acids, etc., with carboxylic acids being particularly preferred. Examples of carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid, etc., with formic acid or acetic acid being particularly preferred. In this disclosure, one organic acid may be used, or two or more may be used in combination. For example, formic acid and acetic acid may be used in combination.

[0519] [Amount of organic acids] The amount of organic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more per 100 parts by weight of the liquid-repellent compound, or 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less. The amount of organic acid may be adjusted so that the pH of the repellent is 3 to 10, for example 5 to 9, particularly 6 to 8. The repellent may be acidic (pH 7 or less, for example 6 or less).

[0520] [Inorganic acid] The repellent agent of this disclosure may contain an inorganic acid. Known inorganic acids can be used. Examples of inorganic acids include hydrogen chloride, hydrogen bromide, hydrogen iodide, nitric acid, boric acid, sulfuric acid, and phosphoric acid. In this disclosure, one inorganic acid may be used, or two or more may be used in combination. Adding an inorganic acid can improve the stability of the aqueous dispersion.

[0521] [Amount of inorganic acid] The amount of inorganic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more per 100 parts by weight of the liquid-repellent compound, or 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less. The amount of inorganic acid may be adjusted so that the pH of the repellent is 3 to 10, for example 5 to 9, particularly 6 to 8. The repellent may be acidic (pH 7 or less, for example 6 or less).

[0522] [Hardening agent] The repellent agents of this disclosure may contain a curing agent (an active hydrogen-reactive compound or an active hydrogen-containing compound). If the repellent agent is for paper (for example, an oil-resistant agent for paper), it does not need to contain a curing agent.

[0523] The curing agent (crosslinking agent) in a repellent can effectively cure the repellent. The curing agent may be an active hydrogen-reactive compound or an active hydrogen-containing compound that reacts with active hydrogen or an active hydrogen-reactive group. Examples of active hydrogen-reactive compounds are isocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds, and hydrazide compounds. Examples of active hydrogen-containing compounds are hydroxyl group-containing compounds, amino group-containing compounds, carboxyl group-containing compounds, ketone group-containing compounds, hydrazide compounds, and melamine compounds.

[0524] The curing agent may contain an isocyanate compound. The isocyanate compound may be a polyisocyanate compound. A polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound acts as a crosslinking agent. Examples of polyisocyanate compounds include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic aliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates. The isocyanate compound may be a blocked isocyanate compound (for example, a blocked polyisocyanate compound). A blocked isocyanate compound is a compound in which the isocyanate groups of an isocyanate compound are masked with a blocking agent to suppress the reaction.

[0525] Examples of aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, and 2,6-diiso These include aliphatic diisocyanates such as cyanatomethyl caproate, and aliphatic triisocyanates such as lysine ester triisocyanate, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, and 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane. These may be used alone or in combination of two or more.

[0526] Examples of alicyclic polyisocyanates include alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of alicyclic polyisocyanates include 1,3-cyclopentene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), and 1,3,5-triisocyanatocyclohexane. These may be used individually or in combination of two or more.

[0527] Examples of aromatic aliphatic polyisocyanates include aromatic aliphatic diisocyanates and aromatic aliphatic triisocyanates. Specific examples of aromatic aliphatic polyisocyanates include 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethylxylylene diisocyanate) or mixtures thereof, and 1,3,5-triisocyanatomethylbenzene. These may be used individually or in combination of two or more.

[0528] Examples of aromatic polyisocyanates include aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates include m-phenylenediisocyanate, p-phenylenediisocyanate, 4,4'-diphenyldiisocyanate, 1,5-naphthalenediisocyanate, 2,4'- or 4,4'-diphenylmethanediisocyanate or mixtures thereof, 2,4- or 2,6-tolylenediisocyanate or mixtures thereof, triphenylmethane-4,4',4''-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate. These may be used individually or in combination of two or more.

[0529] Examples of polyisocyanate derivatives include various derivatives of the polyisocyanate compounds described above, such as dimers, trimers, biuretes, allophanates, carbodiimides, uretodiones, uretoimines, isocyanurates, and iminooxadiazinediones. These may be used individually or in combination of two or more.

[0530] These polyisocyanates can be used individually or in combination of two or more types. It is preferable to use a blocked polyisocyanate compound (blocked isocyanate), which is a compound in which the isocyanate group of a polyisocyanate compound is blocked with a blocking agent, as the polyisocyanate compound. It is preferable to use a blocked polyisocyanate compound because it is relatively stable in solution and can be used in the same solution as the repellent agent.

[0531] Blocking agents sequester free isocyanate groups. Blocked polyisocyanate compounds can be easily reacted with hydroxyl groups by heating them to, for example, 100°C or higher, such as 130°C or higher, which regenerates the isocyanate groups. Examples of blocking agents include phenolic compounds, lactam compounds, aliphatic alcohol compounds, and oxime compounds. Polyisocyanate compounds can be used alone or in combination of two or more.

[0532] Epoxy compounds are compounds that have an epoxy group. Examples of epoxy compounds include epoxy compounds having a polyoxyalkylene group, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether. A chloromethyl group-containing compound is a compound that has a chloromethyl group. Examples of chloromethyl group-containing compounds include chloromethyl polystyrene. Carboxyl group-containing compounds are compounds that have a carboxyl group. Examples of carboxyl group-containing compounds include (poly)acrylic acid and (poly)methacrylic acid.

[0533] Specific examples of ketone group-containing compounds include (poly)diacetone acrylamide and diacetone alcohol. Specific examples of hydrazide compounds include hydrazine, carbohydrazide, and adipic acid hydrazide. Specific examples of melamine compounds include melamine resin and methyl etherified melamine resin.

[0534] [Amount of hardener] The amount of curing agent may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 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, per 100 parts by weight of the liquid-repellent compound, or 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.

[0535] [Other ingredients] The repellent agent may contain other components besides those listed above. Examples of other components include polysaccharides, flocculants, yield enhancers, coagulants, binder resins, anti-slip agents, sizing agents, paper strength enhancers, fillers, antistatic agents, preservatives, UV absorbers, antibacterial agents, deodorizers, and fragrances. These may be used individually or in combination of two or more. In addition to the components mentioned above, other components include water-repellent and / or oil-repellent agents, dispersants, texture modifiers, softeners, flame retardants, paint fixatives, wrinkle inhibitors, drying speed modifiers, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, insect repellents, defoamers, shrinkage inhibitors, wrinkle inhibitors, shape-retaining agents, drape-retaining agents, ironing improvers, whitening agents, whitening agents, fabric softening clay, color transfer inhibitors such as polyvinylpyrrolidone, polymer dispersants, stain removers, scum dispersants, fluorescent whitening agents such as 4,4-bis(2-sulfostyryl)biphenyldisodium (Chiba Specialty Chemicals Chinopearl CBS-X), dye fixatives, and colorfastness inhibitors such as 1,4-bis(3-aminopropyl)piperazine. The following can be incorporated as agents, stain removers, and fiber surface modifiers: enzymes such as cellulase, amylase, protease, lipase, and keratinase; antifoaming agents and substances that can impart the texture and functionality of silk, such as moisture absorption and release properties: silk protein powder, surface modifiers or emulsified dispersions thereof (e.g., K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical), hydrolyzed silk liquid (Jomo), Silkgen G Solubble S (Ichimaru Falcos)); and anti-fouling agents (e.g., nonionic polymer compounds consisting of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units (e.g., FR627 manufactured by Go-o Chemical Industry), SRC-1 manufactured by Clariant Japan, etc.). These may be used individually or in combination of two or more. The components may be appropriately determined according to the intended use of the repellent.

[0536] [Amount of other ingredients] The individual or total amounts of the other components may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, per 100 parts by weight of the liquid-repellent compound, and may also 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.

[0537] <Pulp composition> The pulp composition in this disclosure comprises a liquid-repellent compound and a pulp base material. The pulp composition in this disclosure may have excellent oil resistance.

[0538] The pulp composition in this disclosure is obtained by adding a liquid-repellent compound to a pulp base material. The pulp composition may also be obtained by treating the pulp base material with a liquid-repellent agent containing a liquid-repellent compound, where the amount and composition of the liquid-repellent agent may be adjusted so that each component is in a desired amount. Each component that may be included in the liquid-repellent agent may also be added to the pulp composition separately as an additive.

[0539] The pulp composition in this disclosure does not necessarily have to contain any of the compounds selected from the group consisting of compounds having 8 or more carbon atoms in a fluoroalkyl group, compounds having 8 or more carbon atoms in a perfluoroalkyl group, compounds having 4 or more carbon atoms in a fluoroalkyl group, compounds having 4 or more carbon atoms in a perfluoroalkyl group, compounds having a perfluoroalkyl group, compounds having a fluoroalkyl group, and compounds having a fluorine atom. The pulp composition in this disclosure can impart liquid repellency to a substrate even without containing these fluorine compounds.

[0540] The pH of the pulp composition may be 3 to 10, for example 5 to 9, and particularly 6 to 8, and the amounts of each component may be adjusted to achieve such a pH.

[0541] [Pulp-based material] The pulp composition includes a pulp base material. The pulp base material is composed of pulp, which may be wood pulp, non-wood pulp, recycled paper pulp, etc.

[0542] [Wood pulp] Wood pulp includes coniferous kraft pulp obtained from genera such as fir and pine, and hardwood kraft pulp obtained from genera such as acacia, eucalyptus, beech, and aspen (e.g., poplar). Examples of coniferous kraft pulp include unbleached coniferous kraft pulp (NUKP), bleached coniferous pulp (NBKP), semi-bleached coniferous kraft pulp (NSBKP), and sulfite coniferous pulp. Examples of hardwood kraft pulp include unbleached hardwood kraft pulp (LUKP), bleached hardwood kraft pulp (LBKP), semi-bleached hardwood kraft pulp (LSBKP), and sulfite hardwood pulp. The pulp used may be used alone or in combination. In addition to kraft pulp, there are also softwood kraft pulp and hardwood kraft pulp, as well as mechanical pulps such as stone ground pulp (SGP), pressure stone ground pulp (PGW), refiner ground pulp (RGP), thermo ground pulp (TGP), chemiground pulp (CGP), crushed wood pulp (GP), and thermomechanical pulp (TMP). Furthermore, recycled paper pulp includes disintegrated recycled paper pulp, disintegrated and deinked recycled paper pulp, or disintegrated, deinked and bleached recycled paper pulp, which are manufactured from brown recycled paper, recycled kraft envelopes, recycled magazines, recycled newspapers, recycled flyers, recycled office paper, recycled corrugated cardboard, recycled white recycled paper, recycled Kent paper, recycled imitation paper, recycled land certificates, etc.

[0543] [Non-wood pulp] Examples of non-wood pulps include pulp obtained from bagasse, kenaf, bamboo, linter, cotton, linen, hemp, ramie, straw, esparto, Manila hemp, sisal hemp, jute, flax, ganpi, mitsumata, and kozo.

[0544] [Pulp fiber length] The average fiber length of the pulp is preferably 0.1 mm or more, more preferably 0.3 mm or more, and even more preferably 0.5 mm or more, from the viewpoint of improving oil resistance, and from the viewpoint of ease of manufacture, it is preferably 5.0 mm or less, more preferably 4.0 mm or less, even more preferably 3.0 mm or less, particularly preferably 2.0 mm or less, and most preferably 1.2 mm or less.

[0545] [Pulp fiber width] From the viewpoint of improving oil resistance, the average fiber diameter of the pulp is preferably 5 μm or more, more preferably 10 μm or more, even more preferably 15 μm or more, and also preferably 50 μm or less, more preferably 40 μm or less, and even more preferably 30 μm or less.

[0546] [Form of pulp substrate] The form of the pulp substrate to which 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, bleached or unbleached high-yield pulps such as crushed wood pulp, mechanical pulp or thermomechanical pulp; pulp slurry containing the pulp; and pulp products such as paper, paper containers, and pulp molded articles.

[0547] [Amount of pulp base material] The amount of pulp base material may be 0.1% or more by weight, 0.5% or more by weight, 1% or more by weight, 3% or more by weight, 5% or more by weight, 10% or more by weight, 20% or more by weight, 30% or more by weight, 50% or more by weight, 75% or more by weight, or 90% or more by weight in the pulp composition, and may also be 99% or less by weight, 75% or less by weight, 50% or less by weight, 40% or less by weight, 30% or less by weight, 20% or less by weight, 10% or less by weight, 5% or less by weight, 4% or less by weight, or 3% or less by weight. When the pulp composition is prepared by internal additives, the amount of pulp base material may be 30% or less by weight in the pulp composition, and when the pulp composition is prepared by external additives, the amount of pulp base material may be 75% or more by weight in the pulp composition.

[0548] The amount of 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.

[0549] [Liquid media] 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 (water, or a mixture of water and an organic solvent), particularly water. The liquid medium may also contain a liquid medium derived from a repellent.

[0550] [Amount of liquid medium] The amount of 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 additives, the amount of 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 additives, the amount of liquid medium may be 30% by weight or less, particularly 10% by weight or less in the pulp composition.

[0551] [Liquid repellent compound] The pulp composition contains a liquid-repellent compound. For details on the liquid-repellent compound, refer to the description of the liquid-repellent compound in the section on <Repellents> above.

[0552] [Amount of liquid-repellent compound] The amount of the liquid-repellent compound may be 0.01% by weight or more, 0.03% by weight or more, 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more, relative to the pulp substrate, preferably 0.03% by weight or more, for example 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, or 5.0% by weight or less, preferably 3.0% by weight or less.

[0553] The liquid-repellent compound may be applied as an external additive to the surface of a pulp substrate (e.g., paper, paper containers, pulp molded products, etc.), and the amount of the liquid-repellent compound contained in the coating layer formed by the external additive treatment is 0.01 g / m². 2 More than 0.03g / m 2 More than 0.05g / m 2 More than 0.1g / m 2 More than 0.3g / m 2 More than 0.5g / m 2 Above, or 1.0 g / m 2 The above is sufficient, and also 5.0 g / m 2 Below 4.0g / m 2 Below 3.0g / m 2 Below 2.0g / m 2 Below 1.0g / m 2 Below 0.5g / m 2 Below 0.3g / m 2 The following, or 0.1 g / m² 2 The following is acceptable:

[0554] [Lignin compounds] The pulp composition preferably contains a lignin compound. For details on the lignin compound, refer to the explanation of the lignin compound in the section on <Luceratinizers>.

[0555] [Amount of lignin compounds] The amount of lignin 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 relative to the pulp base material, 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, more preferably 3.0% by weight or less.

[0556] [Dispersant] The pulp composition may contain a dispersant. For details on the dispersant, refer to the explanation of the dispersant in the section on <Water-repellent agents>.

[0557] [Amount of dispersant] The amount of dispersant 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 relative to the pulp substrate, 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, more preferably 3.0% by weight or less.

[0558] [Paper strengthening agent] The pulp composition may contain a paper strength agent. Examples of paper strength agents include: Polyacrylamide-based paper strengthening agents such as cationic polyacrylamide, anionic polyacrylamide, and amphoteric polyacrylamide; Polysaccharide-based paper strengthening agents such as starch, enzyme-modified starch, thermochemically modified starch, oxidized starch, esterified starch, etherified starch (e.g., hydroxyethylated starch), aldehyde-modified starch, cationized starch, starch, xanthan gum, karaya gum, welan gum, guar gum, pectin, tamarind gum, carrageenan, chitosan, gum arabic, locust bean gum, cellulose, alginic acid, agar, dextran, cellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, chitin nanofibers, cellulose nanofibers, and pullulan, and modified polysaccharides thereof (e.g., modified polysaccharides into which hydroxyl groups or cationic groups have been introduced); Polyamide-based paper strengthening agents such as polyamide resins, polyamine resins, polyamide-polyamine resins, polyamide-epichlorohydrin resins, polyamide-polyamine-epichlorohydrin resins, polyamide-polyurea-formaldehyde resins, and epoxidized polyamide resins; Urea / melamine-based paper strengthening agents such as urea resin, melamine resin, urea-formaldehyde resin, and melamine-formaldehyde resin; Polyvinyl alcohol-based paper strengthening agents such as polyvinyl alcohol, fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, cation-modified polyvinyl alcohol, and terminally alkyl-modified polyvinyl alcohol; Examples include styrene-butadiene copolymers, polyvinyl acetate, vinyl chloride-vinyl acetate copolymers, polyvinyl chloride, polyvinylidene chloride, polyacrylic acid esters, fatty acid diamides, polyethyleneimine resins, and ketone aldehyde resins. In this disclosure, polyacrylamide-based paper strength agents, polysaccharide-based paper strength agents, or polyamide-based paper strength agents are preferred.

[0559] [Amount of paper strengthening agent] The amount of paper strength agent may be 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more relative 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.

[0560] [Sizing agent] The pulp composition may contain a sizing agent. Examples of sizing agents include cationic sizing agents, anionic sizing agents, neutral sizing agents, and amphoteric sizing agents, such as rosin-based sizing agents (e.g., acidic rosin-based sizing agents, neutral rosin-based sizing agents), alkyl ketene dimers, and alkenyl succinic anhydride.

[0561] [Amount of sizing agent] The amount of sizing agent may be 0.1% by weight or more, 0.2% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more relative 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.

[0562] [Other additives] In addition to the above, the pulp composition may also contain other additives such as fixatives (water-soluble aluminum compounds such as aluminum sulfate and polyaluminum chloride), coagulants / flocculants (polyamine resins, etc.), yield enhancers (polyacrylamide resins, etc.), organic acids (formic acid, acetic acid, etc.), dyes, slime control agents, and defoamers, which are known paper-use chemicals used in the manufacture of pulp products.

[0563] [Amount of other additives] The amounts of other additives may be 0.01% by weight or more, 0.1% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, respectively, relative to the pulp base material, or 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.

[0564] <Product manufacturing method> The method for manufacturing the product in this disclosure may include a step of treating a substrate with the repellent agent of this disclosure as a treatment agent.

[0565] The substrates treated with the treatment agents in this disclosure are not limited, but are preferably fibrous substrates, and may be particularly textile substrates or pulp substrates, and especially pulp substrates.

[0566] Examples of fiber base materials include natural animal and plant fibers such as cotton, linen, wool, and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers such as rayon and acetate; inorganic fibers such as glass fibers, carbon fibers, and asbestos fibers; or blends thereof. Fiber products include woven fabrics, knitted fabrics, and nonwoven fabrics; fabrics in the form of clothing (e.g., water-repellent clothing, e.g., raincoats) and carpets; however, fibers, yarns, and intermediate fiber products (e.g., slivers or rovings) in their pre-fabric state may also be treated.

[0567] The substrates to be treated with the treatment agent of this disclosure are not limited to fibrous substrates, but can also include stone, filters (e.g., electrostatic filters), dust masks, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster.

[0568] When the substrate is glass, the manufactured glass product may be an optical component. A layer (or film), such as a hard coat layer or an anti-reflective layer, may be formed on the surface (outermost layer) of the glass substrate. Either a single-layer anti-reflective layer or a multi-layer anti-reflective layer may be used for the anti-reflective layer. Examples of inorganic materials that can be used for the anti-reflective layer include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, CeO2, MgO, Y2O3, SnO2, MgF2, and WO3. These inorganic materials may be used individually or in combination of two or more (for example, as a mixture). When a multi-layer anti-reflective layer is used, it is preferable to use SiO2 and / or SiO for the outermost layer. When the article to be manufactured is an optical glass component for a touch panel, a thin film using a transparent electrode, such as indium tin oxide (ITO) or indium zinc oxide, may be present on part of the surface of the substrate (glass). Furthermore, the substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomizing film layer, a hard coating film layer, a polarizing film, a phase difference film, and a liquid crystal display module, depending on its specific specifications.

[0569] [Method of manufacturing pulp products] The pulp products (paper products) in this disclosure can be obtained by treating a pulp substrate with a pulp repellent containing a liquid-repellent compound, and then subjecting the resulting pulp composition to processing steps such as drying, heating, and molding, as necessary. The pulp products may be oil-resistant pulp products that have been treated with an oil-resistant agent.

[0570] The repellent agent in this disclosure can be applied to a pulp substrate by conventionally known methods as a treatment agent (particularly a surface treatment agent). The treatment method may involve diluting the repellent agent in this disclosure by dispersing it in an organic solvent or water as needed, and then applying it to the interior and / or surface of the pulp substrate by known methods such as immersion coating, spray coating, or foam coating, followed by drying. The dilution ratio may be appropriately changed depending on the concentration and application of the repellent agent, but may be 3 to 2000 times, for example, 10 to 100 times. After drying, a pulp product with the solid components of the repellent agent attached is obtained. Furthermore, if necessary, it may be applied together with a suitable crosslinking agent and curing may be performed.

[0571] The repellent can be applied to the pulp substrate by any known method for treating the pulp substrate with a liquid. The pulp substrate may be immersed in the repellent, the pulp substrate and the repellent may be mixed, or the solution may be applied to or sprayed onto the pulp substrate. The treated pulp substrate is preferably dried and cured by heating to develop liquid repellency. The heating temperature may be, for example, 100°C to 200°C, 100°C to 170°C, or 100°C to 120°C. In this disclosure, the heating time may be 5 seconds to 60 minutes, for example, 30 seconds to 3 minutes.

[0572] As a method for processing pulp substrates, an internal processing method in which a repellent is added to the pulp substrate before papermaking (e.g., in the form of a pulp slurry) or an external processing method in which a repellent is applied to the pulp substrate after papermaking (e.g., a pulp product) can be used. Examples of internal processing methods include mixing and immersion, and may include a step of adding a repellent to the pulp slurry and stirring and mixing it. Examples of external processing methods include spraying, coating, immersion, and foam coating, and specifically include a pound-type two-roll size press, a gate-roll type, and a rod-metering size press. The processing may be either external or internal. For example, when the pulp substrate is paper, the paper may be coated, or the solution may be attached to or sprayed onto the paper, or it may be mixed with the pulp slurry before papermaking. When the pulp substrate is a fibrous material, examples of processing methods include padding, immersion, spraying, and coating. For padding treatment, for example, methods using padding equipment described on pages 396-397 of the Dictionary of Textile Dyeing and Processing (published in 1963 by Nikkan Kogyo Shimbun) and pages 256-260 of Color Dyeing Chemistry III (published in 1975 by Jikkyo Shuppan Co., Ltd.) can be used. For coating treatment, for example, methods using coating machines described on pages 473-477 of the General Catalog of Dyeing and Finishing Equipment (published in 1981 by Senryo-sha) can be used. For immersion treatment, for example, methods using batch-type dyeing machines described on pages 196-247 of the General Catalog of Dyeing and Finishing Equipment (published in 1981 by Senryo-sha) can be used, and liquid flow dyeing machines, air flow dyeing machines, drum dyeing machines, winch dyeing machines, washer dyeing machines, cheese dyeing machines, etc. can be used. For spray treatment, for example, methods using air sprays that atomize the treatment liquid with compressed air and spray it, or air sprays using a liquid pressure atomization method can be used.

[0573] The processing method may be an internal additive treatment in which a repellent is added to the pulp slurry before papermaking. The internal additive treatment may include filling the pulp slurry into a mold and allowing the liquid medium to permeate out of the mold to form the pulp. For example, the internal additive treatment may include, but is not limited to, one or more of the following steps: adding a repellent to the pulp slurry and stirring and mixing it; dewatering the pulp composition prepared in the first step by suction through a mesh-like body of a predetermined shape to deposit the pulp composition and form a pulp molded intermediate; and molding and drying the pulp molded intermediate using a heated mold to obtain a pulp molded product. After simple drying at room temperature or high temperature, the processed paper may optionally be heat-treated depending on the properties of the paper. The heat treatment temperature may be 150°C or higher, 180°C or higher, or 210°C or higher, and may be 300°C or lower, 250°C or lower, or 200°C or lower, and may be particularly 80°C to 180°C. By performing heat treatment in such a temperature range, excellent oil resistance and other properties can be obtained. The pulp substrate, which has undergone internal additive treatment, may be further treated externally with a repellent agent, and additional liquid-repellent compounds or repellents may be applied to the surface.

[0574] The processing method may be an external additive treatment in which a repellent is applied to the pulp substrate after papermaking. Size presses for external additive treatment can also be classified as follows depending on the application method. One application method is the so-called pound-type two-roll size press, in which a coating liquid (sizing liquid) is supplied to the nip portion formed by passing paper between two rubber rolls, creating a coating liquid reservoir called a pound, and the sizing liquid is applied to both sides of the paper by passing the paper through this reservoir. Other application methods are the gate-roll type and the rod-metering size press, in which the sizing liquid is applied by a surface transfer type. In the pound-type two-roll size press, the sizing liquid easily penetrates into the interior of the paper, while in the surface transfer type, the sizing liquid components tend to remain on the surface of the paper. Compared to the pound-type two-roll size press, the surface transfer type allows the coating layer to remain on the surface of the paper more easily, and the coating layer formed on the surface is greater than that of the pound-type two-roll size press. In this disclosure, performance can be imparted to the paper even when the former pound-type two-roll size press is used. Paper processed in this manner can exhibit excellent oil resistance and other properties after simple drying at room temperature or high temperature, and optionally, depending on the properties of the paper, undergo heat treatment up to 300°C, for example, up to 200°C, and particularly within a temperature range of 80°C to 180°C.

[0575] Specific examples of pulp products include paper, paper containers, pulp molded articles, food packaging materials, food containers, gypsum board base paper, coated base paper, medium-grade paper, general liners and cores, neutral pure white roll paper, neutral liners, rust-preventive liners and metal interleaving paper, kraft paper, neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper, and neutral information paper. Suitable examples of pulp products include food packaging materials and food containers, and for example, pulp products for food contact applications, particularly pulp molded articles for food contact applications.

[0576] Although embodiments have been described above, it should be understood that various modifications to the form and details are possible without departing from the spirit and scope of the claims. [Examples]

[0577] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to these examples.

[0578] <Testing Method> The examination procedure is as follows:

[0579] [High temperature oil resistance] 100 ml of 65°C evaluation solution (corn oil) was poured into a pulp molded product shaped into a container, and it was left to stand for 45 minutes, or 100 ml of 80°C evaluation solution (corn oil) was poured in, and it was left to stand for 30 minutes, after which the evaluation solution was discarded. The degree to which the evaluation solution soaked into the pulp molded product (container) was visually evaluated according to the following criteria. 4: There are almost no oil stains visible on the inside of the bottom of the container. 3: No oil stains are visible on the outside of the bottom of the container. 2: Oil stains are visible on less than 5% of the outer surface area of ​​the container bottom. 1: Oil stains are visible on 5% to less than 50% of the outer surface area of ​​the container bottom. 0: Oil stains are visible on more than 50% of the outer surface area of ​​the container bottom.

[0580] [Product stability] The stability of the liquid repellent was visually evaluated according to the following criteria after 40g of the liquid repellent was placed in a 50ml glass bottle and left standing at 20°C. ○: Does not settle or separate after 4 weeks. △: Sedimentation and separation do not occur within 1 week, but sedimentation or separation is observed within 4 weeks. ×: Sedimentation or separation is observed within one week.

[0581] <Synthesis Example 1> In a 1L plastic container, 100 parts stearic acid amide ethyl acrylate, 370 parts pure water, 3 parts Nippon Paper Industries' Sun Extract (registered trademark) P252, and 12 parts polyoxyethylene alkyl ether were charged. After heating to 80°C, the mixture was emulsified and dispersed using ultrasound for 15 minutes. The emulsified dispersion was transferred to a 1000cc four-necked flask equipped with a nitrogen inlet tube, thermometer, stirring rod, and reflux tube. After nitrogen purging, 1 part ammonium persulfate was added, and the mixture was reacted at 60°C for 4 hours to obtain an aqueous dispersion of the polymer. Subsequently, pure water was added to prepare an aqueous dispersion (oil resistant agent) with a solid content of 20% by weight.

[0582] <Synthesis Example 2> A 1L polyethylene container was filled with 100 parts stearic acid amide ethyl acrylate, 370 parts pure water, 6 parts Sun Extract P252, and 12 parts polyoxyethylene alkyl ether, and an aqueous dispersion was prepared using the same method as in Synthesis Example 1.

[0583] <Synthesis Example 3> A 1L polyethylene container was filled with 100 parts stearic acid amide ethyl acrylate, 370 parts pure water, 1 part Sun Extract P252, and 12 parts polyoxyethylene alkyl ether, and an aqueous dispersion was prepared using the same method...

Claims

1. It contains liquid-repellent compounds and lignin compounds, A liquid-repellent compound is a compound different from a lignin compound, and is an oil-resistant agent for pulp substrates that satisfies one or more of the following conditions (1) to (4). (1) The lignin compound has an ionic group other than a phenolic hydroxyl group. (2) The liquid-repellent compound is a (meth)acrylic polymer having a chain-like alkyl group with 12 to 18 carbon atoms. (3) The charge density of the oil-resistant agent is -1500 μeq / g or more and 0 μeq / g or less. (4) A (meth)acrylic polymer having 50% by weight or more of repeating units derived from monomer (a1) of the liquid-repellent compound, The monomer (a1) Formula (a1): CH 2 =C(-X a1 )-C(=O)-Y a11 -Z(-Y a12 -R a1 ) n [In the formula, R a1 is each independently a hydrocarbon group having 6 to 40 carbon atoms.] X a1 is a hydrogen atom, a monovalent organic group, or a halogen atom. Y a11 is -O- or -NH-, Each Y a12 is independently composed of a direct bond or at least one group selected from -O-, -C(=O)-, -S(=O)2-, -NH-, or -CH2-. Z is a directly bonded or divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms. n is either 1 or 2. It is a monomer represented by [formula].

2. The oil-resistant agent according to claim 1, wherein the lignin compound has an ionic group other than a phenolic hydroxyl group.

3. The oil-resistant agent according to claim 1 or 2, wherein the lignin compound is a lignin sulfonate.

4. The oil-resistant agent according to claim 1 or 2, wherein the lignin compound is sodium ligninsulfonate.

5. The oil-resistant agent according to claim 1 or 2, wherein the liquid-repellent compound is a compound having at least one selected from the group consisting of a hydrocarbon group having 6 or more carbon atoms, which may have substituents, and a polysiloxane group.

6. The oil-resistant agent according to claim 5, wherein the liquid-repellent compound is at least one selected from the group consisting of vinyl polymers, amine modifiers, polyol modifiers, polycarboxylic acid modifiers, isocyanate derivatives, waxes, and silicones.

7. The oil-resistant agent according to claim 5, wherein the liquid-repellent compound is at least one selected from the group consisting of (meth)acrylic polymers, styrene polymers, polysiloxane group-containing (meth)acrylic polymers, hydrocarbon waxes, polyurethanes, silicone resins, fatty acid esters, fatty acid amides, and modified starches.

8. The oil-resistant agent according to claim 1 or 2, wherein the liquid-repellent compound is a (meth)acrylic polymer having a chain-like alkyl group with 12 to 18 carbon atoms.

9. The oil-resistant agent according to claim 1 or 2, wherein the hexadecane contact angle of the liquid-repellent compound is 25° or more.

10. The oil resistant agent according to claim 1 or 2, wherein the charge density of the oil resistant agent is -1500 μeq / g or more and 0 μeq / g or less.

11. The liquid-repellent compound is a (meth)acrylic polymer having 50% by weight or more of repeating units derived from monomer (a1), The monomer (a1) Formula (a1): CH 2 =C(-X ａ１ )-C(=O)-Y ａ１１ -Z(-Y ａ１２ -R ａ１ ) ｎ [In the formula, R ａ１ Each of these is independently a hydrocarbon group having 6 to 40 carbon atoms. X ａ１ is a hydrogen atom, a monovalent organic group, or a halogen atom. Y ａ１１ is -O- or -NH-, Y ａ１２ These are independent of each other, and can be directly bonded, or -O-, -C(=O)-, -S(=O) ２ -, -NH- or -CH ２ - A base consisting of at least one selected from, Z is a directly bonded or divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms. n is either 1 or 2. The oil-resistant agent according to claim 1 or 2, wherein the monomer is represented by .

12. An oil-resistant pulp product comprising an oil-resistant agent according to claim 1 or 2, wherein the liquid-repellent compound and the lignin compound are attached to a pulp substrate.

13. The oil-resistant pulp product according to claim 12, wherein the amount of the liquid-repellent compound is 0.03% by weight or more and 3.0% by weight or less relative to the pulp base material.

14. The oil-resistant pulp product according to claim 12, which is a pulp molded product.

15. The oil-resistant pulp product according to claim 12, which is a food packaging material or food container.

16. A method for producing an oil-resistant pulp product, comprising the step of treating a pulp base material with an oil-resistant agent described in claim 1 or 2 by external or internal additive treatment.

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