Agent for imparting oil resistance

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] The present disclosure relates to repellents, particularly oil repellents. [Background technology]

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

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-237795 Summary of the Invention [Problem to be solved by the invention]

[0004] Patent Document 1 does not describe or suggest the imparting of oil resistance to a pulp base material or the use of the compound as an oil-resistant agent.

[0005] An object of the present disclosure is to provide a novel oil-proofing agent that can impart oil resistance to a substrate (particularly a pulp substrate). [Means for solving the problem]

[0006] The present disclosure includes the following aspects: [Section 1] An oil-resistant agent comprising a liquid-repellent compound and a lignin compound. [Section 2] Item 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] Item 3. The oil-resistant agent according to Item 1 or 2, wherein the lignin compound is a lignin sulfonate. [Section 4] Item 4. The oil-proofing agent according to any one of Items 1 to 3, wherein the lignin compound is sodium lignosulfonate. [Section 5] Item 5. The oil-resistant agent according to any one of Items 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 a substituent, and a polysiloxane group. [Section 6] Item 6. The oil-resistant agent according to Item 5, wherein the liquid-repellent compound is at least one selected from the group consisting of vinyl polymers, amine-modified compounds, polyol-modified compounds, polycarboxylic acid-modified compounds, isocyanate derivatives, waxes, and silicones. [Section 7] Item 7. The oil-resistant agent according to Item 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] Item 8. The oil-resistant agent according to any one of Items 1 to 7, wherein the liquid-repellent compound is a (meth)acrylic polymer having a chain alkyl having 12 to 18 carbon atoms. [Section 9] Item 9. The oil-resistant agent according to any one of items 1 to 8, wherein the liquid-repellent compound has a contact angle with hexadecane of 25° or more. [Section 10] Item 10. The oil-resistant agent according to any one of items 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 a 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 are 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—, Y a12 are each independently a direct bond or a group consisting of at least one selected from -O-, -C(=O)-, -S(=O)2-, -NH-, and -CH2-, Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms; n is 1 or 2. 3. The oil-resistant agent according to claim 1, wherein the monomer is a monomer represented by the formula: [Section 12] Item 11. An oil-resistant pulp product, comprising the oil-proofing agent according to any one of Items 1 to 10, and a liquid-repellent compound and a lignin compound attached to a pulp substrate. [Section 13] Item 12. 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. [Section 14] Item 14. The oil-resistant pulp product according to Item 12 or 13, which is a pulp molded product. [Section 15] 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. [Section 16] Item 12. A method for producing an oil-resistant pulp product, comprising a step of treating a pulp base material with the oil-proofing agent according to any one of items 1 to 11 by external or internal addition. [Effects of the Invention]

[0007] According to the present disclosure, oil resistance can be imparted to a substrate (particularly a pulp substrate). DETAILED DESCRIPTION OF THE INVENTION

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

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

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

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

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

[0013] Because the adhesion of chemicals to the surface of a pulp substrate is a reversible reaction, it is believed that the application of shear makes it difficult for adhesion to be maintained. In particular, prolonged stirring is likely to be detrimental to chemical fixation because shear is continuously applied. Despite this, the inventors have unexpectedly discovered that by using the repellent agent of the present disclosure, even when the pulp slurry after adding the repellent agent is stirred for a long period of time (e.g., 30 minutes or more), the product (e.g., pulp mold) exhibits excellent high-temperature oil resistance.

[0014] The repellent of the present disclosure contains a liquid-repellent compound described below as an active ingredient. The liquid-repellent compound may be used by itself as a repellent, or may be used in combination with other ingredients as a repellent. Furthermore, the repellent of the present disclosure preferably contains a lignin compound described below. By including a lignin compound, the effects of the present disclosure can be effectively achieved.

[0015] The repellent agent of the present disclosure may not contain any compound selected from the group consisting of a compound having a fluoroalkyl group having 8 or more carbon atoms, a compound having a perfluoroalkyl group having 8 or more carbon atoms, a compound having a fluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group, a compound having a fluoroalkyl group, and a compound having a fluorine atom. The repellent agent of the present disclosure can impart liquid repellency to a substrate even if it does not contain these fluorine compounds.

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

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

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

[0019] The average particle size obtained from a scanning electron microscope image of particles obtained by removing the liquid medium from a water-dispersed composition of the present disclosure (e.g., an oil-resistant agent for pulp) 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, or 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, a grinder, homogenizer, or the like may be used to micronize the particles in the raw material and / or dispersion. The room temperature is 20°C to 30°C, particularly 25°C.

[0020] The ionic charge density in the repellent of the present 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, 200 μeq / g or more, preferably -600 μeq / g or more, for example, -400 μeq / g or more, -200 μeq / g or more, -50 μeq / g or more, and may also be 5000 μeq / g or less. , 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 one preferred aspect, 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] A sample liquid with a solid content of 0.1 g / L is used to measure the anion demand using a particle charge meter (BTG MUTEK PCD-06) with a 1 / 1000 N potassium polyvinyl sulfonate solution, and the ionic charge density (cationic charge density) is calculated using the following formula (1). Alternatively, the cation demand is measured in the same way using a polydiallyldimethylammonium chloride solution instead of potassium polyvinyl sulfonate, and the ionic charge density (anionic charge density) is calculated using the following formula (1). Ionic charge density (μeq / g) = A / B (1) A: Cation demand or anion demand (μeq / L) B: Sample liquid concentration (g / L)

[0022] [Lignin Compounds] The repellent of the present disclosure contains a lignin compound. By including the lignin compound, the effects of the present disclosure can be effectively achieved. For example, by including the lignin compound, the stability of the repellent when it is made into an aqueous dispersion can be improved.

[0023] In the present disclosure, the lignin compound is a compound selected from lignin and modified lignin. The modified lignin is a compound whose main component is a structure derived from lignin, in which a portion of the lignin has been chemically modified and / or decomposed into smaller molecules, and may be a lignin derivative, a decomposition product of lignin, a derivative of a decomposition product of lignin, or the like. Specific examples of lignin compounds include lignin, lignosulfonic acid, kraft lignin, soda lignin, soda-anthraquinone lignin, organosolv lignin, explosive lignin, and sulfuric acid lignin. Of these, lignosulfonic 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 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 aspect, 1.5 to 6.0%, 1.6 to 5.5%, or 1.7 to 5.0%. Furthermore, when the lignin compound is kraft lignin, the amount of phenolic hydroxyl groups is more preferably 2.0% or more, 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, the ionization differential spectrum is obtained by subtracting the absorption spectrum of a neutral solution containing lignin at the same concentration from the absorption spectrum of an alkaline solution containing the lignin sample (lignin compound), and the difference spectrum is calculated using the following formula: Phenolic hydroxyl group content (%) = 17 × Δαmax / 4100 × 100 The phenolic hydroxyl groups (%) are calculated from the above. Δαmax [L / (g·cm)] indicates the differential absorption coefficient. For details, refer to Nakano Junzo (ed.), "Lignin Chemistry - Fundamentals and Applications - Revised and Enlarged Edition," Uni Publishing, 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, and preferably 1,000 or more, and may be 500,000 or less, 300,000 or less, 100,000 or less, 50,000 or less, or 30,000 or less, and preferably 50,000 or less. The weight average molecular weight may be a polyethylene glycol-equivalent molecular weight measured by GPC.

[0027] The lignin compound may have a functional group (particularly an ionic group) other than a phenolic hydroxyl group. Examples of such a functional group include a hydroxyl group, a carboxyl group, a polyalkylene oxide chain, a sulfonic acid group, a nitroxyl group, a carbonyl group, a phosphate group, an amino group, an epoxy group, a methylol group, a cyanate group, an isocyanate group, a vinyl group, and a maleimide group. An ionic group is particularly preferred, and an anionic group is preferable. This can further improve dispersibility. Examples of such functional groups include a carboxyl group, a sulfonic acid group, and a phosphate group. Among these, a sulfonic acid group is more preferable.

[0028] Lignin compounds have 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 a sulfur-containing functional group such as a sulfo group or a thiol group, and the sulfur content may be 0.1% by mass or more, 0.3% by mass or more, 0.5% by mass or more, or 6% by mass or less, 5% by mass or less, 4% by mass or less, or 3% by mass or less.

[0030] The functional groups in the lignin compound can be quantitatively or qualitatively measured by instrumental analysis such as NMR, IR, and elemental analysis.

[0031] The lignin compound may contain structural units derived from other compounds, such as (alkyl)phenols (e.g., phenol and cresol), aromatic hydrocarbon compounds (e.g., benzene and naphthalene), etc., within the scope of the present disclosure.

[0032] It is difficult to uniformly specify the chemical structure of lignin compounds using a general formula or the like because the skeleton that constitutes lignin compounds has a very complex molecular structure.

[0033] The lignin compound may be in the form of a salt, for example, an alkali metal salt such as a sodium salt or a potassium salt, an alkaline earth metal salt such as a calcium salt, an ammonium salt, or a salt of an organic amine.

[0034] [Lignosulfonic acid] The lignin compound is preferably lignin sulfonic acid, which is a lignin compound modified with a sulfo group, and may be, for example, a compound having a skeleton in which a carbon atom at the α-position of the side chain of the hydroxyphenylpropane structure of lignin is cleaved to introduce a sulfo group.

[0035] The lignosulfonic acid may be a lignosulfonate salt, and examples of the salt include alkali metal salts such as sodium salts or potassium salts, alkaline earth metal salts such as calcium salts, ammonium salts, and salts of organic amines, such as sodium lignosulfonate.

[0036] As the lignin sulfonic acid, commercially available products may be used, such as Vanilex HW (manufactured by Nippon Paper Industries Co., Ltd.), Sunex M (manufactured by Nippon Paper Industries Co., Ltd.), Pearlex NP (manufactured by Nippon Paper Industries Co., Ltd.), Sunflow RH (manufactured by Nippon Paper Industries Co., Ltd.), POLYFON, and REAX (all manufactured by Ingevity). As the sodium lignin sulfonate, commercially available products may be used, such as Sunex (registered trademark) P252 and Vanilex (registered trademark) N manufactured by Nippon Paper Industries Co., Ltd., and Polyfon (registered trademark) F, Polyfon (registered trademark) T, Polyfon (registered trademark) O, and Polyfon (registered trademark) H manufactured by Ingevity.

[0037] The amount of the 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, relative to 100 parts by weight of the liquid repellent compound, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less.

[0038] [Liquid repellent compound] The repellent agent of the present disclosure includes a liquid repellent compound that adheres to a substrate (particularly a pulp substrate) and imparts liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or stain resistance, particularly oil resistance, to the substrate.

[0039] [Characteristics, etc.] The properties that the liquid repellent compound may have are listed 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 be 100° or less, 90° or less, or 75° or less. When the liquid-repellent compound has an HD contact angle equal to or greater than the above lower limit, it can impart good liquid repellency (especially oil repellency) to the substrate. The HD contact angle is the static contact angle of the liquid-repellent compound with a spin-coated film, and is obtained by dropping 2 μL of HD onto the spin-coated film at room temperature (25° C.) and measuring the contact angle 1 second after the drop has landed.

[0041] The water contact angle of the liquid-repellent compound may be 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 65° or more, 75° or more, 85° or more, 90° or more, or 100° or more, and may be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. When the liquid-repellent compound has a water contact angle equal to or greater than the above lower limit, it can impart good liquid repellency (particularly water repellency) to the substrate. The water contact angle is the static contact angle of the liquid-repellent compound with respect to a spin-coated film, and is obtained by dropping 2 μL of water onto the spin-coated film at room temperature (25° C.) and measuring the contact angle one second after the drop has landed.

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

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

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

[0046] The liquid repellent compound in the present disclosure may not be a fatty acid ester having a glycosidic bond. A fatty acid ester having a glycosidic bond is typically a compound having a structure in which a fatty acid is attached to a hydroxy group of a compound having a glycosidic bond (typically a sugar (monosaccharide or polysaccharide)) via an ester bond.

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

[0048] (Optionally substituted hydrocarbon group having 6 or more carbon atoms) The liquid repellent compound may have a hydrocarbon group having 6 or more carbon atoms which may have a substituent.

[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 (an alkyl group, an alkenyl group, etc.). The hydrocarbon group may be branched, cyclic, or linear, and is more preferably linear.

[0050] The hydrocarbon group is 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, a hydrocarbon compound (e.g., hydrocarbon wax) is understood to consist of only a monovalent hydrocarbon group and one hydrogen atom, and for example, an n-alkane (eicosane) having 20 carbon atoms is understood to consist of only an alkyl group having 20 carbon atoms 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 be 75 or less, 65 or less, 60 or less, 50 or less, 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 40 or less, 30 or less, 25 or less, or 20 or less, and in one aspect, 6 or more and 60 or less, 6 or more and 40 or less, 12 or more and 30 or less, or 12 or more and 20 or less. The number of carbon atoms in the hydrocarbon group is typically 6 or more and 40 or less, but may be more than 40, for example, when the liquid repellent compound is a hydrocarbon compound (hydrocarbon wax).

[0052] The hydrocarbon group may have a substituent, but is preferably unsubstituted. Examples of the substituent include -OR', -N(R')2, -COOR', and a halogen atom (wherein R' is, independently in each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have an active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the substituted hydrocarbon group, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less. For example, the hydrocarbon group may have 1 to 3 (for example, 1) -OR' (particularly -OH) as a substituent (for example, other than at the terminal).

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

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

[0055] The number of silicon atoms in 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, and is preferably 10 or more, and may be 50,000 or less, 25,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 3,000 or less, 1,500 or less, 1,000 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less, for example, 500 or less.

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

[0057] The polysiloxane group has the formula: -[-Si(R s )2-O-] a - [In the formula, R s is independently in each occurrence a hydrocarbon group or a reactive group having 1 to 40 carbon atoms; a is an integer between 5 and 10,000. It may be expressed as:

[0058] R s is 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 hydrocarbon groups having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group (particularly aliphatic hydrocarbon groups, particularly alkyl groups such as a methyl group or an ethyl group, particularly a methyl group).

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

[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, and is preferably 10 or more, and may be 10,000 or less, 7,500 or less, 5,000 or less, 3,000 or less, 1,500 or less, 1,000 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less, and is preferably 500 or less.

[0064] In the polysiloxane group, R is a hydrocarbon group having 1 to 5 carbon atoms. s The quantity of R s It 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 be 100 mol% or less, 90 mol% or less, 80 mol% or less, or 70 mol% or less, based on the total of R s Based on the total number of groups, 50 mol % or more may be methyl groups or ethyl groups (particularly methyl groups).

[0065] In the polysiloxane group, R is a hydrocarbon group having 6 to 40 carbon atoms. s The quantity of R s and may be 100 mol % or less, 90 mol % or less, 80 mol % or less, or 70 mol % or less, based on the total of

[0066] In the polysiloxane group, the reactive group R s The quantity of R s The polysiloxane group may be 5 mol % or more, 10 mol % or more, 20 mol % or more, or 30 mol % or more, and may be 50 mol % or less, 40 mol % or less, 30 mol % or less, or 20 mol % or less, based on the total of the reactive groups R s may not include.

[0067] R s The groups may be introduced randomly or in blocks, but are preferably introduced randomly.

[0068] The terminal structure of the polysiloxane group is not limited, but may be -R s , -OR s , -Si(R s )3, etc. The R sThe reactive group may or may not have one or more reactive groups. Examples of the reactive group are as described above, and may be, for example, at least one selected from the group consisting of an epoxy ring, a hydroxy group, a (meth)acrylic group, and a carboxyl group.

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

[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 is independently in each occurrence a hydrocarbon group or a reactive group having 1 to 40 carbon atoms; R s 50 mol % or more of the total groups are methyl groups, L s1 is independently in each occurrence a hydrocarbon group having 1 to 20 carbon atoms; a is between 5 and 10,000. TIFF2025114516000001.tif2169 [In the formula, a represents an integer of 0 to 150, b represents an integer of 1 to 150, (a+b) is 5 to 200, and n is an integer of 0 to 36.] etc.

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

[0072] [Examples of liquid-repellent compounds] The liquid-repellent compound may be at least one selected from the group consisting of vinyl polymers, amine-modified compounds, polyol-modified compounds, polycarboxylic acid-modified compounds, isocyanate derivatives, waxes, and silicones, such as 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 hydrocarbon groups having 6 or more carbon atoms and polysiloxane groups, which may have a substituent. Details of the liquid-repellent compound will be described below.

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

[0074] The liquid-repellent compound may contain an ester group, an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfonamide group, a sulfoneurea group, a sulfoneurethane group, or a sulfonimide group (e.g., an ester group, an amide group, a urethane group, a urea group, or an imide group). For example, the liquid-repellent compound may contain -C(=O)-O-, -OC(=O)-, -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'-, or -SONR'- (where R' is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms)). The liquid-repellent compound may be a compound obtained by bonding a raw material compound and a modifying group (particularly the monovalent hydrocarbon group optionally having the above-mentioned substituent) via at least one of these groups. The liquid-repellent compound may contain an amide structure. When the liquid-repellent compound contains at least an amide structure, the liquid repellency can be improved. Here, the amide structure may be a broad amide structure and may be selected from amide (acid amide) groups (or carboxylic acid amides), urethane groups, urea groups, imide groups, thioamide groups, thiourethane groups, thiourea groups, thioimide groups, sulfonamide groups, sulfoneurethane groups, sulfoneurea groups, sulfonimide groups, etc. The amide structure may be an amide structure selected from the group consisting of -(C=O)N(-)2, -(C=S)N(-)2, and -S(=O)2N(-)2 (note that each group may be inverted). Here, at least one of the bonds possessed by 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 in a group selected from the group consisting of an amide group, a urethane group, a urea group, and an imide group.

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

[0076] [Vinyl polymer] As an example of a liquid-repellent compound, a vinyl polymer will be described. A vinyl polymer is a polymer obtained by polymerizing a vinyl monomer, and exhibits liquid-repellency. Here, the vinyl monomer may 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, a vinylene group, a vinylidene group, an acryloyl group, a methacryloyl group, or a derivative group thereof.

[0077] [Characteristics, etc.] The vinyl polymer is preferably a compound containing carbon of biobased origin. The biobased content is measured in accordance with ASTM D6866. The biobased content of the vinyl polymer may be 20% or more, preferably 30% or more, more preferably 50% or more, even more preferably 60% or more, even more preferably 70% or more, and most preferably 80% or more or 90% or more, for example, 100%. A high biobased content means that the amount of fossil resource-based materials, such as petroleum, used is reduced. From this perspective, the higher the biobased content of the vinyl polymer, the better.

[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 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 3,000 or more, 5,000 or more, 10,000 or more, 30,000 or more, 100,000 or more, 300,000 or more, or 500,000 or more, and may be 5,000,000 or less, 3,000,000 or less, 1,000,000 or less, 750,000 or less, 500,000 or less, 300,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, or 5,000 or less. The weight average molecular weight may be a polystyrene-equivalent molecular weight measured by GPC.

[0080] (a) Hydrocarbon group-containing monomer The vinyl polymer may have a repeating unit derived from a hydrocarbon group-containing monomer (a), which 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, and may have, for example, 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. The above explanation (hydrocarbon group having 6 or more carbon atoms, which may have a substituent) is used here, but it is preferable that the monomer (a) has no substituent. Here, the hydrocarbon group is a monovalent group. The hydrocarbon group contained in monomer (a) may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be branched or linear, and is more preferably linear. The hydrocarbon group may be saturated or unsaturated. The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group (alkyl group). The number of carbon atoms in the hydrocarbon group may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, preferably 10 or more, 12 or more, 14 or more, or 16 or more, and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, 25 or less, or 20 or less.

[0083] The monomer (a) having a hydrocarbon group having 6 to 40 carbon atoms is formula: CH2=C(-X a )-C(=O)-Y a (R a ) k [In the formula, R a are each independently a hydrocarbon group having 6 to 40 carbon atoms, X a is a hydrogen atom, a monovalent organic group, or a halogen atom, Y a is a group consisting of at least one selected from a divalent to tetravalent hydrocarbon group having one carbon atom (particularly, —CH—, —CH(—)), —CH—, —O—, —C(═O)—, —S(═O)—, and —NH—; k is 1 to 3. It is preferable that the monomer is a monomer represented by the following formula:

[0084] X aX may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. a Examples of X are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, and a cyano group. a is preferably a hydrogen atom, a methyl group, or a chlorine atom. a is particularly preferably a hydrogen atom.

[0085] Y a is a divalent to tetravalent group. a is preferably a divalent group. Y a is preferably a group composed of at least one selected from a hydrocarbon group having one carbon atom, -C6H4-, -O-, -C(=O)-, -S(=O)2-, and -NH-. a is preferably not a hydrocarbon group. Examples of hydrocarbon groups having one carbon atom include -CH2-, -CH(-)2, and -C(-)3. When hydrocarbon groups having one carbon atom are repeatedly linked together, -(CH2) m A hydrocarbon group having two or more carbon atoms may be formed, such as Y - (where m is an integer of 1 to 5). a 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'- wherein Y′ is a direct bond, —O—, —NH—, or —S(═O)—; R' is -(CH2) m - (m is an integer of 1 to 5) or -C6H4- (phenylene group). It may be.

[0087] Y aSpecific examples thereof include -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- [where 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 of 1 to 5, particularly 2 or 4.] It is preferable that Y a is -O- or -O-(CH2) m -NH-C(=O)-, especially -O-(CH2) m It is more preferably -NH-C(=O)-.

[0089] R a are each independently a hydrocarbon group having 6 to 40 carbon atoms, and although the above explanation of (hydrocarbon group having 6 or more carbon atoms which may have a substituent) is used, it is preferably a linear or branched hydrocarbon group. The hydrocarbon group may particularly be a linear hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, and especially an alkyl group. The hydrocarbon group preferably has 12 to 30 carbon atoms, for example, 12 to 18, 16 to 26, or 15 to 26, particularly 18 to 22, or 17 to 22.

[0090] Specific examples of the monomer (a) are: Formula (a1): CH2=C(-X a1 )-C(=O)-Y a11 -Z(-Y a12 -R a1 ) n [In the formula, R a1 are each 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 is —O— or —NH—, Y a12 are each independently a direct bond or a group consisting of at least one selected from -O-, -C(=O)-, -S(=O)2-, -NH-, and -CH2-, Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms; n is 1 or 2. A monomer represented by the formula: Formula (a2): CH2=C(-X a2 )-C(=O)-Y a2 -R a2 [In the formula, R a2 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 is —O— or —NH—.] Monomers represented by is.

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

[0092] The monomer (a1) may be a monomer having a hydrocarbon group having 6 to 40 carbon atoms and an NH group-containing group. The 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. When the monomer (a1) contains such a group, the effects of the present disclosure can be effectively achieved.

[0093] The monomer (a1) is a (meth)acrylate or (meth)acrylamide having at least one group selected from -O-, -C(=O)-, -S(=O)2-, -NH-, and -CH2-.

[0094] The monomer (a1) has the formula: CH2=C(-X a1 )-C(=O)-Y a11 -Z(-Y a12 -R a1 ) n [In the formula, R a1 are 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—, Y a12 are each independently a direct bond or a group consisting of at least one selected from -O-, -C(=O)-, -S(=O)2-, -NH-, and -CH2-, Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms; n is 1 or 2. The compound may be represented by the formula: Y a12 and / or Z may not be a direct bond. a12 and Z may not be a direct bond at the same time.

[0095] R a1 is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. a1 In the formula (I), the hydrocarbon group preferably has 12 to 30 carbon atoms, for example, 16 to 26 or 15 to 26, and particularly preferably 18 to 22 or 17 to 22 carbon atoms.

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

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

[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 of 1 to 5.] is.

[0099] Especially Y a12 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 preferred that Y is -NH-C(=O)-, -C(=O)-NH-, -OC(=O)-NH-, -NH-C(=O)-O- or -NH-C(=O)-NH-. a12 may not be a direct bond.

[0101] Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and may have a straight-chain or branched structure. Z preferably has 2 to 4 carbon atoms, and particularly 2 carbon atoms. Specific examples of Z include a direct bond, -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH(-)2, -CH2(CH-)CH2-, -CH2CH2CH(-)2, -CH2CH2CH2CH2CH(-)2, -CH2CH2(CH-)CH2-, and -CH2CH2CH2CH(-)2. Z does not have to be a direct bond.

[0102] 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 Preferably, R a1 and X a1 has the same meaning as above.] Monomer (a1) is CH2=C(-X a1 )-C(=O)-O-(CH2) m -NH-C(=O)-R a1 It is particularly preferred that:

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

[0104] Preferred examples of the monomer (a) are as follows: Stearyl (meth)acrylate, behenyl (meth)acrylate, stearyl alpha chloroacrylate, behenyl alpha chloroacrylate; Stearyl (meth)acrylamide, Behenyl (meth)acrylamide;

[0105] TIFF2025114516000002.tif2453

[0106] TIFF2025114516000003.tif2253 TIFF2025114516000004.tif2152 TIFF2025114516000005.tif2155

[0107] TIFF2025114516000006.tif2357 TIFF2025114516000007.tif2256 TIFF2025114516000008.tif2156

[0108] TIFF2025114516000009.tif2051 TIFF2025114516000010.tif2054 TIFF2025114516000011.tif2352 TIFF2025114516000012.tif2659

[0109] TIFF2025114516000013.tif2046

[0110] TIFF2025114516000014.tif2249 [In the above formula, n is a number from 6 to 40, and m is a number from 1 to 5.] The compound of the above chemical formula is an acrylic compound in which the α-position is a hydrogen atom, but specific examples include a methacrylic compound in which the α-position is a methyl group and an α-chloroacrylic compound in which the α-position is a chlorine atom.

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

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

[0113] R a12 R is the same as the hydrocarbon group contained in the monomer (a) described above, and is a hydrocarbon group having 6 to 40 carbon atoms, preferably an alkyl group, and examples thereof include chain hydrocarbon groups and cyclic hydrocarbon groups. Among these, a chain hydrocarbon group is preferred, and a linear saturated hydrocarbon group is particularly preferred. a12 The number of carbon atoms is 6 or more and 40 or less, preferably 11 to 27, and particularly preferably 15 to 23.

[0114] R a13 R is a hydrocarbon group having 1 to 5 carbon atoms, preferably an alkyl group. The hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched, and may have an unsaturated bond, but is preferably linear. a13 The number of carbon atoms in R is preferably 2 to 4, and particularly preferably 2. a13 is preferably an alkylene group.

[0115] The amide group-containing monomer is R a12 There is only one type (for example, R a12 is only a compound having 17 carbon atoms), or R a12 is a combination of multiple a12 and a compound having 17 carbon atoms, R a12 and a compound having 15 carbon atoms).

[0116] An example of an amide group-containing monomer is a carboxylic acid amide alkyl (meth)acrylate. Specific examples of the amide group-containing monomer include palmitic acid amidoethyl (meth)acrylate, stearic acid amidoethyl (meth)acrylate, behenic acid amidoethyl (meth)acrylate, myristate amidoethyl (meth)acrylate, laurate amidoethyl (meth)acrylate, isostearate ethyl amido(meth)acrylate, oleic acid ethyl amido(meth)acrylate, tert-butylcyclohexylcaproic acid amidoethyl (meth)acrylate, adamantanecarboxylic acid ethyl amido(meth)acrylate, naphthalenecarboxylic acid amidoethyl (meth)acrylate, anthracenecarboxylic acid amidoethyl (meth)acrylate, palmitic acid amidopropyl (meth)acrylate, stearic acid amidopropyl (meth)acrylate, palmitic acid amidoethyl vinyl ether, stearic acid amidoethyl vinyl ether, palmitic acid amidoethyl allyl ether, stearic acid amidoethyl allyl ether, and mixtures thereof.

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

[0118] (a2) Monomer The monomer (a2) has the formula: CH2=C(-X a2 )-C(=O)-Y a2 -R a2 [In the formula, R a2 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 is —O— or —NH—.] It is a compound represented by the formula:

[0119] Monomer (a2) is Y a2 a long chain acrylate ester monomer in which Y is —O—; a2 is a long-chain acrylamide monomer in which is -NH-. R a2 is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. a2 In the formula (I), the hydrocarbon group preferably has 12 to 30 carbon atoms, for example, 16 to 26 carbon atoms, and particularly preferably 18 to 22 carbon atoms. X a2 may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group, and is preferably a hydrogen atom, a methyl group, or a chlorine atom.

[0120] Preferred specific examples of the long-chain acrylate ester monomer are lauryl (meth)acrylate, stearyl (meth)acrylate, icosyl (meth)acrylate, behenyl (meth)acrylate, stearyl alpha chloroacrylate, icosyl alpha chloroacrylate, and behenyl alpha chloroacrylate. Specific preferred examples of the long-chain acrylamide monomer are stearyl (meth)acrylamide, icosyl (meth)acrylamide, and behenyl (meth)acrylamide.

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

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

[0123] The hydrophilic group is preferably an oxyalkylene-containing group (the alkylene group has 2 to 6 carbon atoms), and particularly preferably an oxyethylene group. In particular, the monomer (b) is preferably an oxyalkylene (meth)acrylate, for example, 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 is —O— or —NH—, R b are each independently an alkylene group having 2 to 6 carbon atoms, A b is a hydrogen atom, an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, or CH2=CX b C(=O)-present, and n is an integer from 1 to 90. It is preferable that the oxyalkylene (meth)acrylate is an oxyalkylene (meth)acrylate represented by the following formula:

[0125] Examples of monomers (b) are those of the 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 are each independently a hydrogen atom or a methyl group, R b are each independently an alkylene group having 2 to 6 carbon atoms, A bi are each 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 ] (monomer (b1), monomer (b2), and monomer (b3) respectively).

[0126] n may be, for example, 1 to 50, particularly 1 to 30, and especially 1 to 15 or 2 to 15. Alternatively, n may be, for example, 1. R b may be a linear or branched alkylene group, for example, of the formula -(CH) x -or-(CH2) x1 -(CH(CH3)) x2 -[wherein x1 and x2 are 0 to 6, for example, 2 to 5, and the sum of x1 and x2 is 1 to 6. -(CH2) x1 - and -(CH(CH3)) x2 The order of - is not limited to the depicted formula and may be random. -(R b O) n In -, R may be two or more types (for example, two to four types, particularly two types), and -(R b O) n- is, for example, -(R 1 O) n1 -and-(R 2 O) n2 -[wherein, R 1 and R 2 are different from each other and are alkylene groups having 2 to 6 carbon atoms, n1 and n2 are numbers of 1 or more, and the sum of n1 and n2 is 2 to 90.

[0127] R in formulas (b1), (b2) and (b3) b is particularly preferably an ethylene group, a propylene group, or a butylene group, and particularly preferably a butylene group. b R may be a combination of two or more alkylene groups. In this case, it is preferable that at least one of R is an ethylene group, a propylene group, or a butylene group. b Examples of the combination include an ethylene group / propylene group combination, an ethylene group / butylene group combination, and a propylene group / butylene group combination. The monomer (b) may be a mixture of two or more types. In this case, at least one of the monomers (b) is a mixture of R in formula (b1), (b2), or (b3). b is preferably an ethylene group, a propylene group, or a butylene group. When using a polyalkylene glycol di(meth)acrylate represented by formula (b2), it is not preferable to use it alone as the monomer (b), but it is preferable to use it in combination with the monomer (b1). In that case, it is also preferable to keep the content of the compound represented by formula (b2) to less than 30% by weight of the monomer (b) used.

[0128] Specific examples of the monomer (b) include, but are not limited to, the following: CH2=CHCOO-CH2CH2O-H CH2=CHCOO-CH2CH2CH2O-H CH2=CHCOO-CH2CH(CH3)OH CH2=CHCOO-CH(CH3)CH2O-H CH2=CHCOO-CH2CH2CH2CH2O-H <h2 style=";text-align:left;direction:ltr">CH2=CHCOO-CH2CH2CH(CH3)OH<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-CH2CH(CH3)CH2O-H<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-CH(CH3)CH2CH2O-H<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-CH2CH(CH2CH3)OH<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-CH2C(CH3)2O-H<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-CH(CH2CH3)CH2O-H<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-C(CH3)2CH2O-H<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-CH(CH3)CH(CH3)OH<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-C(CH3)(CH2CH3)OH<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-(CH2CH2O)2-H<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-(CH2CH2O)4-H<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-(CH2CH2O)5-H<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-(CH2CH2O)6-H<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-(CH2CH2O)5-CH3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-(CH2CH2O)9-CH3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-(CH2CH2O)<h2 style=";text-align:left;direction:ltr"> 23 <h2 style=";text-align:left;direction:ltr"> -CH3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-(CH2CH2O)<h2 style=";text-align:left;direction:ltr"> 90 <h2 style=";text-align:left;direction:ltr"> -CH3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0129] <h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-(CH2CH(CH3)O)9-H<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-(CH2CH(CH3)O)9-CH3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-(CH2CH(CH3)O)<h2 style=";text-align:left;direction:ltr"> 12 <h2 style=";text-align:left;direction:ltr"> -CH3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-(CH2CH2O)5-(CH2CH(CH3)O)2-H<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9<h2 style=";text-align:left;direction:ltr"> 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] The monomer (b) is X 2 is a hydrogen atom. Monomer (b) is particularly preferably hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or hydroxyethyl acrylamide.

[0137] (c) Ionic group-containing monomer The vinyl polymer may contain a repeating unit derived from an ionic group-containing monomer (c). The monomer (c) is preferably a monomer (particularly, an acrylic monomer) containing one ethylenically unsaturated double bond and an ionic group. 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, and may have, for example, a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond.

[0139] Examples of the monomer having an anionic group include a monomer having a carboxyl group, a sulfonic acid group, or a phosphoric acid group. Specific examples of the monomer having an anionic group include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, vinylsulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, (meth)acrylate phosphate, vinylbenzenesulfonic acid, acrylamido-tertiarybutylsulfonic acid, and salts thereof.

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

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

[0142] The cationic group in the form of a salt is a salt with an acid (organic acid or inorganic acid). Organic acids, such as carboxylic acids having 1 to 20 carbon atoms (particularly monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and stearic acid), are preferred. Dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate and salts thereof are preferred.

[0143] Specific examples of the monomer having a cationic group are as follows: CH2=CHCOO-CH2CH2-N(CH3)2 and its salts (e.g. acetate) CH2=CHCOO-CH2CH2-N(CH2CH3)2 and its salts (e.g. acetate) CH2=C(CH3)COO-CH2CH2-N(CH3)2 and its salts (e.g. acetate) CH2=C(CH3)COO-CH2CH2-N(CH2CH3)2 and its salts (e.g. acetate salts) CH2=CHC(O)N(H)-CH2CH2CH2-N(CH3)2 and its salts (e.g. acetate) CH2=CHCOO-CH2CH2-N(-CH3)(-CH2-C6H5) and its salts (e.g. acetate) CH2=C(CH3)COO-CH2CH2-N(-CH2CH3)(-CH2-C6H5) and its salts (e.g. acetate) CH2=CHCOO-CH2CH2-N + (CH3)3Cl - CH2=CHCOO-CH2CH2-N + (-CH3)2(-CH2-C6H5)Cl - CH2=C(CH3)COO-CH2CH2-N + (CH3)3Cl - CH2=CHCOO-CH2CH(OH)CH2-N + (CH3)3Cl - CH2=C(CH3)COO-CH2CH(OH)CH2-N + (CH3)3Cl - CH2=C(CH3)COO-CH2CH(OH)CH2-N + (-CH2CH3)2(-CH2-C6H5)Cl - CH2=C(CH3)COO-CH2CH2-N + (CH3)3Br - CH2=C(CH3)COO-CH2CH2-N + (CH3)3I - CH2=C(CH3)COO-CH2CH2-N + (CH3)3O - SO3CH3 CH2=C(CH3)COO-CH2CH2-N + (CH3)(-CH2-C6H5)2Br -

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

[0146] (e) Crosslinkable monomer The vinyl polymer may contain a repeating unit derived from a 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 the reactive group include a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group, and a carboxyl group.

[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 monomer The vinyl polymer may have a repeating unit derived from a cyclic hydrocarbon group-containing monomer (f). The cyclic hydrocarbon group-containing monomer (f) is a monomer having a cyclic hydrocarbon group, and may be a monomer having one ethylenically unsaturated double bond and a cyclic hydrocarbon group. The vinyl polymer may be a styrene polymer having a repeating unit 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, and may, for example, 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 a monocyclic group, a polycyclic group, or a bridged ring group, with a bridged ring group being preferred. The cyclic hydrocarbon group may have a chain group (for example, a halogen atom, a linear or branched chain hydrocarbon group (particularly a linear or branched chain hydrocarbon group having 1 to 20 carbon atoms)).

[0152] The cyclic hydrocarbon group may have 4 or more, 6 or more, or 8 or more carbon atoms, and may have 30 or less, 26 or less, 22 or less, 18 or less, or 14 or less carbon atoms.

[0153] Specific examples of cyclic hydrocarbon groups include cyclohexyl, t-butylcyclohexyl, adamantyl, 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl, bornyl, isobornyl, norbornyl, dicyclopentanyl, dicyclopentenyl, benzyl, phenyl, naphthyl, 2-t-butylphenyl, residues obtained by removing one or more hydrogen atoms from these groups (e.g., cyclohexylene, adamantylene, phenylene, naphthylene, etc.), and groups that are substitution products thereof.

[0154] Specific examples of the cyclic hydrocarbon group-containing monomer (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 in which these acrylates are substituted with acrylamide, etc. These may be used alone or in combination of two or more.

[0155] An example of the cyclic hydrocarbon group-containing monomer (f) is a styrene compound. The styrene compound may be modified with a chain 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 thereof include styrene, 4-t-butylstyrene, 3,5-di-t-butylstyrene, 2,4,6-tri-t-butylstyrene, 4-methylstyrene, 3,5-dimethylstyrene, and 2,4,6-trimethylstyrene. The styrene compound may be an α-methylstyrene compound or an α-chlorostyrene compound in which the α-position is a chlorine atom, or may be a styrene compound in which the α-position is a hydrogen atom.

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

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

[0158] The polysiloxane group contained in the monomer (g) is described above in relation to the polysiloxane group. The monomer (g) may have a polydimethylsiloxane group on its side chain.

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

[0160] Monomer (g) is formula: CH2=C(-X g )-C(=O)-Y g (R) g k [In the formula, R g is a group having a polydimethylsiloxane group, X g is a hydrogen atom, a monovalent organic group, or a halogen atom, Y g is a group consisting of at least one selected from a divalent to tetravalent hydrocarbon group having one carbon atom (particularly, —CH—, —CH(—)), —CH—, —O—, —C(═O)—, —S(═O)—, and —NH—; k is 1 to 3. It is preferable that the monomer is a monomer represented by the following formula:

[0161] X g X may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. g Examples of X are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, and a cyano group. g is preferably a hydrogen atom, a methyl group, or a chlorine atom. g is particularly preferably a hydrogen atom.

[0162] Y g is a divalent to tetravalent group. g is preferably a divalent group. Y gis preferably a group composed of at least one selected from a hydrocarbon group having one carbon atom, -C6H4-, -O-, -C(=O)-, -S(=O)2-, and -NH-. g is preferably not a hydrocarbon group. Examples of hydrocarbon groups having one carbon atom include -CH2-, -CH(-)2, and -C(-)3. When hydrocarbon groups having one carbon atom are repeatedly linked together, -(CH2) m A hydrocarbon group having two or more carbon atoms may be formed, such as Y - (where m is an integer of 1 to 5). g 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'- wherein Y′ is a direct bond, —O—, —NH—, or —S(═O)—; R' is -(CH2) m - (m is an integer of 1 to 5) or -C6H4- (phenylene group). It may be.

[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 -S(=O)2-NH- (wherein m is 1 to 5, particularly 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 of 1 to 5, particularly 2 or 4.] It is preferable that Yg is -O- or -O-(CH2) m -NH-C(=O)-, especially -O-(CH2) m It is more preferably -NH-C(=O)-.

[0166] R g is a group having a polydimethylsiloxane group, and the above explanation of (polysiloxane group) is applied to the polydimethylsiloxane group.

[0167] Examples of the monomer (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, the respective symbols are as defined above.]

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

[0169] [Polymer composition] The combination of the monomers (a) to (g) constituting the repeating units of the vinyl polymer is not particularly limited, but examples are as follows (brackets are omitted): a a+b 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 combination, the monomer (g) may be used in place of or in addition to the monomer (a). Another monomer (g) may be used in the above combination. For pulp products, it is preferable to use the monomer (a), the monomer (b), and the monomer (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, and may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the vinyl polymer.

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

[0172] The amount of monomer (a1) in monomer (a) may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, or 80% by weight or more, and is preferably 30% by weight or more, and may 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] The amount of monomer (a2) in monomer (a) may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, or 80% by weight or more, and may 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 be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the vinyl polymer. The amount of the repeating units derived from monomer (b) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, 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, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the 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, and may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the vinyl polymer. The amount of the repeating units derived from monomer (c) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, 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, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the 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, based on the vinyl polymer; and the amount of repeating units derived from monomer (d) may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the vinyl polymer. The amount of the repeating units derived from monomer (d) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, 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, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the repeating units derived from monomer (a).

[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, and may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the vinyl polymer. The amount of the repeating units derived from monomer (e) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, 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, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the 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 be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the vinyl polymer. The amount of the repeating units derived from monomer (f) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, 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, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the repeating units derived from monomer (a).

[0179] The amount of repeating units derived from monomer (g) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, and may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the vinyl polymer. The amount of the repeating units derived from monomer (g) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, 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, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the repeating units derived from monomer (a).

[0180] The amount of repeating units derived from 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 be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the vinyl polymer. The amount of the repeating units derived from monomer (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, 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, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the repeating units derived from monomer (a).

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

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

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

[0184] The organic solvent is inert to the monomers and dissolves them, and may be, for example, an ester (e.g., an ester having 2 to 40 carbon atoms, specifically, ethyl acetate, butyl acetate), a ketone (e.g., a ketone having 2 to 40 carbon atoms, specifically, methyl ethyl ketone, diisobutyl ketone, methyl isobutyl ketone), or an alcohol (e.g., an alcohol having 1 to 40 carbon atoms, specifically, ethanol, butanol, isopropyl alcohol). Specific examples of the organic solvent include acetone, chloroform, 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, relative to 100 parts by weight of the total of the monomers.

[0185] Emulsion polymerization involves emulsifying monomers in water in the presence of a polymerization initiator and an emulsifier, purging with nitrogen, and then polymerizing the mixture at 50-80°C for 1-20 hours with stirring. Polymerization initiators include water-soluble initiators such as benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, sodium peroxide, potassium persulfate, and ammonium persulfate, as well as oil-soluble initiators such as azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount of 0.01-10 parts by weight per 100 parts by weight of monomer.

[0186] To obtain a polymer aqueous dispersion with excellent shelf stability, it is desirable to polymerize the monomer by microparticulating it in water using an emulsifying device capable of applying powerful crushing energy, such as a high-pressure homogenizer or ultrasonic homogenizer. Furthermore, various anionic, cationic, or nonionic emulsifiers can be used as emulsifiers, and are used in an amount ranging from 0.5 to 20 parts by weight per 100 parts by weight of the monomer. It is preferable to use anionic and / or nonionic and / or cationic emulsifiers. If the monomers are not completely compatible, it is preferable to add a compatibilizer, such as a water-soluble organic solvent or a low-molecular-weight monomer, that will fully compatibilize these monomers. Addition of a compatibilizer can improve emulsifiability and copolymerizability.

[0187] The water-soluble organic solvent may be any of the organic solvents described above. Examples include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, and ethanol. These may be used in an amount of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, per 100 parts by weight of water. Examples of low-molecular-weight monomers include methyl methacrylate, glycidyl methacrylate, and 2,2,2-trifluoroethyl methacrylate. These may be used in an amount of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, per 100 parts by weight of the total amount of monomers.

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

[0189] [Amine-modified compounds] As an example of the liquid-repellent compound, an amine-modified compound will be described. The amine-modified compound is a compound obtained by chemically modifying an amine compound so as to exhibit liquid-repellent properties.

[0190] Due to their structure, the amine-modified compounds disclosed herein have excellent dispersibility in liquid media, and the repellents disclosed herein can have stable performance. Repellents that use polymeric compounds as active ingredients tend to have broad molecular weight distributions and contain relatively large amounts of impurities. On the other hand, amine-modified compounds can be made into low-molecular-weight compounds, narrowing (uniformizing) the molecular weight distribution, and can therefore 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 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 product of the present disclosure may not have an active hydrogen-containing group. Examples of the active hydrogen-containing group include an amino group (an amino group that is not adjacent to a carbonyl group, e.g., a primary or secondary amino group), a hydroxyl group, and a carboxyl group. In particular, the amine-modified product of the present disclosure may not have a primary or secondary amino group that is not adjacent to a carbonyl group.

[0193] The amine-modified product in the present disclosure may be a polyamide having a plurality of amide structures, for example, a polyamide having a plurality of modifying groups (for example, Z N ) may be a polyamide modified via an amide structure. Here, the amide may be an amide structure contained in a urethane group, a urea group, an imide, or the like.

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

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

[0196] For details of the optionally substituted hydrocarbon group having 6 or more carbon atoms or the polysiloxane group, the above descriptions of the optionally substituted hydrocarbon group having 6 or more carbon atoms and the polysiloxane group are incorporated herein by reference.

[0197] (amine skeleton) The amine-modified product of the present disclosure has an amine skeleton. The amine skeleton has one or more amino groups with a predetermined number of bonds (valence) obtained by removing a predetermined number of atoms or atomic groups (e.g., hydrogen) from an amine compound. The amino group in the amine skeleton refers to a group selected from the group consisting of -NH, -NH-, and -N(-) and includes amino groups adjacent to carbonyl groups contained in amide groups, urethane groups, urea groups, imides, etc. Note that the amine skeleton may be any aliphatic or aromatic group having one or more amino groups, and does not exclude the presence of heteroatoms other than nitrogen.

[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 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 be 100 or less, 80 or less, 60 or less, 40 or less, 30 or less, 20 or less, 10 or less, or 5 or less, preferably 50 or less, particularly 30 or less.

[0200] The amine skeleton has one or more amino groups. The amino groups are monovalent to trivalent amino groups, and are one or more groups selected from the group consisting of -NH2, -NH-, and -N(-)2. The number of amino groups in the amine skeleton may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, preferably 2 or more, and may be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1.

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

[0202] The amine skeleton may be composed of a monovalent to trivalent amino group and a chain saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group which may be interrupted by an oxygen atom and / or a sulfur atom.

[0203] The molar ratio of carbon atoms to nitrogen atoms (C / N ratio) in the amine skeleton may be 1 or more, 2 or more, 2.5 or more, 3 or more, 3.5 or more, or 4 or more, and may be 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3.5 or less, 3 or less, 2.5 or less, or 2 or less, and is preferably 6 or less or 4 or less.

[0204] (-Y N -Z N n ) The amine modification in the present disclosure has the formula: -Y N -Z N n [In the formula, Y Nis a direct bond or a group with a valence of 1+n, Z N represents a monovalent hydrocarbon group having 6 to 40 carbon atoms or a monovalent polysiloxane group which may have a substituent, n is an integer between 1 and 3. and having one or more groups represented by At least one -Y N -Z N n may be bonded to a nitrogen atom of the amine skeleton.

[0205] Amine modification 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 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 modification N -Z N n is bonded to the nitrogen atom of the amine skeleton. N -Z N n Among the number of -Y bonded to the nitrogen atom of the amine skeleton, N -Z N n The proportion of the number of -Y groups not bonded to a nitrogen atom of the amine skeleton may be 10% or more, 30% or more, 60% or more, 80% or more, or 100%, and may be 100% or less, 95% or less, 75% or less, 50% or less, or 25% or less. N -Z N n may be bonded to other groups (for example, hydrocarbon groups) carried by the amine skeleton.

[0207] (Y N ) Y N is a direct bond or a 1+n valent group, preferably a 1+n valent group. N is an amine skeleton and n ZN It acts as a linker connecting the

[0208] n is Y N Z combines with N and may be an integer of 1 or more and 3 or less. n may be 1 or more, 2 or more, or 3 or more, or 3 or less, 2 or less, or 1 or less, for example, 2 or less.

[0209] Y N may be an aliphatic group (unsaturated or saturated) 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 be 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, or 300 or less.

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

[0212] Y N represents a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2, -N(-)2, a divalent to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a divalent to tetravalent hydrocarbon aromatic ring, and a divalent to tetravalent heterocycle. [In the formula, R' is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms)] It may be a (1+n) valent group consisting of one or more groups selected from the group consisting of:

[0213] Y N is Y N1 and Y N2 is a (1+n) valent group consisting of one or more members selected from the group consisting of Y N1 is a group consisting of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2, and -N(-)2 (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms)), Y N2 is a group consisting of one or more members selected from the group consisting of di- to tetravalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms, di- to tetravalent hydrocarbon aromatic rings, and di- to tetravalent heterocycles, In this specification, Y N The group shown as follows has an amine skeleton on the left and Z on the right. N Combine with.

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

[0215] Y N1 is a direct bond or a divalent or higher valent group. N1The valence of Y may be 2 to 4, 2 to 3, or 2. N1 is preferably not only a direct bond.

[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 be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0217] Y N1 may be one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2, and -N(-)2 (wherein R', in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms)). Y N1 Examples include: direct binding, -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, —C(═O)—NR′—, —C(═O)—NR′—C(═O)—, -C(=NR')-, -S-, -SO2-, -SO2NR'-, -C(OR')R'-, -C(OR')(-)2, -N(-)2 etc. [In the formula, R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).] In addition, Y N1 is bonded to a nitrogen atom of the amine skeleton, the nitrogen atom is considered to be part of the amine skeleton (amino group).

[0218] 〇 Y N2 Y N2 is a linker of a hydrocarbon ring which may have a substituent, a hydrocarbon aromatic ring which may have a substituent, or a heterocyclic ring which may have a substituent.

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

[0220] Y N2 is a divalent or higher valent group. N2 The valence of may be, for example, 2 to 4, 2 to 3, or 2.

[0221] Y N2 may have 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 carbon atoms, 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.

[0222] Y N2 is composed of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent hydrocarbon aromatic rings, and optionally substituted di- to tetravalent heterocycles.

[0223] The di- to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or straight-chain hydrocarbon group. The di- to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group having 1 to 40 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more, and may be 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less. The valence of the aliphatic hydrocarbon group may be 2 or more, 3 or more, or 4 or less, 3 or less, or 2.

[0224] The aliphatic hydrocarbon group may have a substituent. Examples of the substituent include -OR', -N(R')2, -COOR', and a halogen atom (wherein R', in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have an active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the substituted aliphatic hydrocarbon group, the 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.

[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-constituting atoms of the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12, and preferably 5 to 12. The valence of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0226] The hydrocarbon aromatic ring may have a substituent. Examples of the substituent include -R', -OR', -N(R')2, -COOR', and a halogen atom (wherein R', in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have an active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the substituted hydrocarbon aromatic ring, the 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.

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

[0228] The heterocycle may have a substituent. Examples of the substituent include -R', -OR', -N(R')2, -COOR', and a halogen atom (wherein R', in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have an active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the substituted heterocycle, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, for example, 65 mol% or more, and 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.] etc.

[0230] Y N2 Specific examples include: -(CH2) p - (p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and having an unsaturated bond; a hydrocarbon group having a branched structure and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms; -(CH2) q -Cy-(CH2) r -(q and r each independently represent a number from 0 to 20, for example, 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle). etc.

[0231] Y N Examples Y N In the following, R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20, 1 to 10, or 1 to 4 carbon atoms).

[0232] Y N An example of this is Y N If is bivalent, -Y N1 -, -Y N1 -Y N2 -, -Y N1 -Y N2 -Y N1 -, -Y N1 -Y N2 -Y N1 -Y N2 -, -Y N2 -, -Y N2 -Y N1 -, -Y N2 -Y N1 -Y N2 -, -Y N2 -Y N1 -Y N2 -Y N1 -, etc.

[0233] Y N An example of this is Y N If 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 Preferred examples of -Y N1 -, -Y N1 -Y N2 -, -Y N1 -Y N2 -Y N1 -, -Y N1 -Y N2 (-)2, -Y N2 -, -Y N2 -Y N1 -, -Y N2 -Y N1 -Y N2 -, -Y N2 -Y N1 (-)2, In the amine-modified compound, one or more Y N However, it is preferred that the terminal on the amine skeleton side is -(C=O)- and that the bond is with a nitrogen atom in the amine skeleton.

[0236] Y N is preferably -Y N1 -, -Y N1 -Y N2 -, -Y N1 -Y N2 -Y N1 -, -Y N1 -Y N2 (-)2, -Y N2 -, -Y N2 -Y N1 -, -Y N2 -Y N1 -Y N2 -, -Y N2 -Y N1 (-)2, [In the formula, Y N1 but independently in each occurrence, direct binding, -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, or -C(=O)-NR'- -C(=O)-NR'-C(=O)- (In the formula, R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).) and Y N2 is a divalent to tetravalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, or a divalent aromatic group (for example, a divalent phenyl group or a divalent triazole group). This makes it possible to impart good liquid repellency to the substrate.

[0237] Y N Further specific examples of *-(C=O)- —O—(C═O)—NR′— [wherein * means bonding to a nitrogen atom of an amine skeleton, R' is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). etc.

[0238] (Z N ) Z N represents a monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, or a monovalent polysiloxane group, and the above explanations for (the hydrocarbon group having 6 or more carbon atoms which may have a substituent) and (the polysiloxane group) are incorporated herein by reference.

[0239] [Examples of amine-modified compounds] (Amine Modification Example 1) Examples of amine-modified compounds include those of the following formula: N(-Y N -Z N n ) p (-H) q -L1 -[N(-Y N -Z N n ) r (-H) s -L 1 -] t -N(-Y N -Z N n ) p (-H) q [In the formula, Y N is independently in each occurrence a direct bond or a group with a valence of 1+n; Z N is independently in each occurrence an optionally substituted linear or branched monovalent hydrocarbon group having from 6 to 40 carbon atoms, L 1 is independently in each occurrence a divalent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms, which may be interrupted by an oxygen atom and / or a sulfur atom; n, in each occurrence, is independently an integer between 1 and 3, inclusive; p, in each occurrence, is independently an integer between 0 and 2, inclusive; q, independently in each occurrence, is an integer between 0 and 2, inclusive; p+q is the sum of each N(-Y N -Z N n ) p (-H) q In, 2, r is independently in each occurrence 0 or 1; s is independently in each occurrence 0 or 1; r+s is the sum of each N(-Y N -Z N n ) r (-H) s In, 1, the sum of all p's and all r's is greater than or equal to 1, t is an integer between 0 and 10. Examples of the compound include a compound represented by the following formula (amine modified example 1):

[0240] In the amine modified example 1, Y N , Z N For details of , and n, the above explanation is cited.

[0241] In the amine modified example 1, L 1 L is a divalent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms, which may be interrupted by oxygen atoms and / or sulfur atoms, and may be a cyclic, branched, or straight-chain hydrocarbon group, and is preferably a straight-chain hydrocarbon group or an aromatic hydrocarbon. 1 The hydrocarbon group in the above description of the [amine skeleton] may be used as L, and the hydrocarbon group may be separated by oxygen atoms and / or sulfur atoms, or may consist of only carbon atoms, nitrogen atoms, and hydrogen atoms. 1 L may be, for example, a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 hydrocarbon aromatic rings. 1 is preferably a cyclic group having both a ring (e.g., an aromatic ring) and a chain structure (e.g., a linear structure, ether oxygen, or thioether sulfur), and specific examples thereof include a 1,3-phenylenebisalkylene group, a 1,4-phenylenebisalkylene group, a diphenyletherdiyl group, and a diphenylthioetherdiyl group. 1 may have 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more carbon atoms, and may be 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, or 3 or less carbon atoms.

[0242] In Amine Modification Example 1, p, in each occurrence, is independently an integer of 0 to 2, inclusive; q, in each occurrence, is independently an integer of 0 to 2, inclusive; and p+q is the sum of the values of each N(-Y N -Z N n ) p (-H) q In the formula, p is 2. Preferably, p may be independently in each occurrence 1 or more, for example 2.

[0243] In Amine Modification Example 1, r is independently in each occurrence 0 or 1, s is independently in each occurrence 0 or 1, and r+s is independently in each occurrence 0 or 1. N -Z N n ) r (-H) s In the formula, p is 1. Preferably, p may be independently in each occurrence 1 or more, for example 2.

[0244] The sum of all p's and all r's is 1 or greater, i.e., Amine Modification Example 1 contains one or more -Y N -Z N n The sum of all p's and all r's may be 1 or more, 3 or more, 5 or more, 7 or more, 9 or more, 12 or more (the sum of all q's and all s'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 Modification Example 1, t is an integer of 0 or more and 10 or less. t may be 0 or more, 1 or more, 2 or more, 4 or more, or 6 or more, and is preferably 0 or more or 2 or more, 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 Modification Example 2) Other examples of amine modifications include those of the formula: N(-Y N -Z N n ) p (-H) q -L 2 (-Y N -Z N n ) u [In the formula, Y N is independently in each occurrence a direct bond or a group with a valence of 1+n; Z N is independently in each occurrence an optionally substituted linear or branched monovalent hydrocarbon group having from 6 to 40 carbon atoms, L2 represents a 1+u-valent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms, which may be interrupted by an oxygen atom and / or a sulfur atom, n, in each occurrence, is independently an integer between 1 and 3, inclusive; p is an integer between 0 and 2, q is an integer between 0 and 2, p+q is 2, u is an integer between 1 and 3, The sum of p and u is greater than or equal to 1.] An example of the compound represented by the formula (amine modified compound example 2) is:

[0247] In the amine modification example 2, Y N , Z N For details of and n, the above explanation is cited.

[0248] In the amine modification example 2, L 2 is a 1+u valent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms, which may be interrupted by oxygen atoms and / or sulfur atoms, and may be a cyclic, branched, or straight-chain hydrocarbon group, preferably a straight-chain hydrocarbon group or an aromatic hydrocarbon. 2 The hydrocarbon group in the above description of the [amine skeleton] may be used as L, and the hydrocarbon group may be separated by oxygen atoms and / or sulfur atoms, or may consist of only carbon atoms, nitrogen atoms, and hydrogen atoms. 2 L may be, for example, a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 hydrocarbon aromatic rings. 2 is preferably a cyclic group having both a ring (e.g., an aromatic ring) and a chain structure (e.g., a linear structure, ether oxygen, or thioether sulfur), and specific examples thereof include a 1,3-phenylenebisalkylene group, a 1,4-phenylenebisalkylene group, a diphenyletherdiyl group, and a diphenylthioetherdiyl group. 2may have 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more carbon atoms, and may be 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, or 3 or less.

[0249] In the amine modification example 2, p is an integer of 0 or more and 2 or less, q is an integer of 0 or more and 2 or less, and p+q is 2. Preferably, p may be 1 or more, for example, 2.

[0250] In the amine modification example 2, u is an integer of 1 or more and 3 or less. u is 1, 2, or 3, for example, 2 or 3.

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

[0252] (Example) Specific examples of the amine-modified compound include compounds represented by the following formula: N is used as a reference.

[0253] TIFF2025114516000015.tif4050

[0254] TIFF2025114516000016.tif3568

[0255] TIFF2025114516000017.tif4746

[0256] TIFF2025114516000018.tif2844

[0257] TIFF2025114516000019.tif2664

[0258] TIFF2025114516000020.tif2554

[0259] TIFF2025114516000021.tif2765

[0260] The amine-modified wax may be a synthetic wax derived from animal or vegetable oils. The synthetic wax may be obtained by condensing a fatty acid derived from animal or vegetable oils with an aliphatic amine or an aromatic amine. Examples of synthetic waxes include fatty acid amide compounds such as hydroxy fatty acid amide compounds, palmitic acid amide compounds, octadecanoic acid amide compounds, stearic acid amide compounds, arachidic acid amide compounds, behenic acid amide compounds, lignoceric acid amide compounds, oleic acid amide compounds, linoleic acid amide compounds, α-linolenic acid amide compounds, γ-linolenic acid amide compounds, arachidonic acid amide compounds, eicosapentaenoic acid amide compounds, and docosahexaenoic acid amide compounds.

[0261] [Manufacturing method] The method for producing the amine-modified product is not limited, but may be carried out by reacting various amines (raw material amines) with Z in the presence of a condensing agent as needed. N A method for synthesizing by reacting a carboxylic acid containing a Z group with various amines. N Examples of the synthesis method include a method of reacting a group-containing carboxylic acid with an acid chloride, acid anhydride, isocyanate, etc. The condensing agent may be a known condensing agent, such as DCC, EDCI, CDI, BOP, COMU, DMT-MM, DPPA, or Py-Bop.

[0262] (Amine (raw material amine)) Examples of amines (raw material amines) that are precursors of the amine skeleton are those that can constitute the amine skeleton, and include alkylamines such as methylamine, ethylamine, propylamine, butylamine, and dibutylamine; alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, pentanediamine, hexamethylenediamine, cyclohexanediamine, and methylenebiscyclohexylamine; diethylenetriamine, triethylenetetramine, tris(2-aminoethyl)amine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tris(2-aminopropyl)amine, tetrapropylenepentamine, pentapropylenehexamine, iminobispropylamine, dibutylenetriamine, bis(2-aminoethoxy)ethane, bis(2-aminoethyl)ether, bis[2-(2-aminoethoxy)ethyl]ether, and bis[2-(3-aminoprotoxy)ethyl] polyalkylenepolyamines such as ether, spermine, and spermidine; oxygen- or sulfur-containing aliphatic amines such as 1-aminopropanediol, 2-amino-1,3-propanediol, 3-amino-1,2-propanediol, polyoxypropylenediamine, and polyoxyethylenediamine; aromatic monoamines such as aniline, 1- or 2-naphthylamine, 1-, 2-, or 9-aminoanthracene, 9-aminophenanthracene, and 2-, 3-, or 4-aminobiphenyl; monocyclic aromatic polyamines such as o-, m-, or p-phenylenediamine, o-, m-, or p-xylylenediamine, diaminotoluene, and 2,3-, 2,4-, or 2,5-tolylenediamine;Diaminobiphenyl, bisaminophenoxyphenylpropane, diaminodiphenyl ether, diaminodiphenyl sulfide, diaminodiphenyl sulfone, diaminobenzophenone, diaminodiphenylmethane, diaminophenylpropane, diaminophenylhexafluoropropane, diaminophenyl phenylethane, bisaminophenoxybenzene, bisaminobenzoylbenzene, bisaminodimethylbenzylbenzene, aminophenoxybiphenyl, aminophenoxyphenylketone, bisaminoditrifluoromethylbenzylbenzene, aminophenoxyphenyl sulfone, aminophenoxyphenyl ether, aminophenoxyphenylpropane, bis(aminophenoxybenzoyl)benzene, bis(aminophenoxy-α,α-dimethylbenzyl)benzene, bis[(aminoaryloxy)benzoyl]diphenyl ether, bis(amino-α,α-dimethylbenzylphenoxy)benzophenone, aminophenoxyphenyl sulfide, bis[amino-α, α-dimethylbenzylphenoxy]diphenyl sulfone, 4,4'-bis[aminophenoxyphenoxy]diphenyl sulfone, diaminodiaryloxybenzophenone, Polycyclic aromatic polyamines such as diaminoaryloxybenzophenone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diaminotriphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-methylenebisaniline, 4,4'-oxydianiline, 1,3-bis(4-aminophenoxy)benzene, 4,4'-diaminodiphenyl ether, and 4,4'-bis(aminophenyl)amine; oxygen- or sulfur-containing polycyclic aromatic polyamines such as 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 3,4'-diaminodiphenyl ether, and 4,4'-diaminodiphenyl sulfide;Examples of the polyamine include hydroxyl group-containing polyamines such as 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, and di-2-hydroxypropylethylenediamine. The polyamine may be a polymerized product of a polymerizable compound such as allylamine.

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

[0264] For details of the optionally substituted hydrocarbon group having 6 or more carbon atoms or the polysiloxane group, the above descriptions of the optionally substituted hydrocarbon group having 6 or more carbon atoms and the polysiloxane group are incorporated herein by reference.

[0265] [Structure etc.] The polyol-modified product may be a polymer having a degree of polymerization of at least 1. From the viewpoint of improving liquid repellency, the degree of polymerization of the polyol-modified product may be at least 2, at least 3, at least 5, at least 6, preferably at least 7, more preferably at least 8, and even more preferably at least 9, and from the viewpoint of improving the handleability of the repellent, it may be at most 100, preferably at most 50, more preferably at most 30, and even more preferably at most 15. The degree of polymerization refers to the number of repeating monomer units constituting the polymer.

[0266] The degree of polymerization in the present disclosure refers to an average degree of polymerization. The average degree of polymerization in the present disclosure refers to polymerization obtained by measurement under the following conditions. When the polyol-modified product in the present disclosure is a polyglycerol-modified product obtained by modifying polyglycerol, the degree of polymerization of the polyol-modified product refers to the average degree of polymerization of the polyglycerol. The average degree of polymerization of the polyglycerol is the average degree of polymerization (n) calculated from the hydroxyl value by end group analysis. Specifically, the average degree of polymerization and the average molecular weight are calculated from the following formulas (Formula 1) and (Formula 2). (Formula 1) Average molecular weight = 74n+18 (Equation 2) Hydroxyl value = 56110(n+2) / average molecular weight The hydroxyl value in the above formula (2) is a numerical value that indicates the number of hydroxyl groups contained in polyglycerol. The hydroxyl value is calculated from the amount of potassium hydroxide required to neutralize the acetic acid required to acetylate the free hydroxyl groups contained in 1 g of polyglycerol, and is calculated in accordance with the "Standard Test Methods for the Analysis of Fats, Oils, and Related Compounds (I) 2003 Edition" compiled by the Japan Oil Chemists' Society. The hydroxyl value of the raw material polyglycerol is measured according to the above Standard Test Methods for the Analysis of Fats, Oils, and Related Compounds, and the average degree of polymerization and average molecular weight of the polyglycerol can be calculated from the above formula.

[0267] When the polyol-modified product in the present disclosure is a polyvinyl alcohol-modified product obtained by modifying polyvinyl alcohol, the degree of polymerization of the polyol-modified product refers to the average degree of polymerization of the polyvinyl alcohol, which can be measured in accordance with JIS K 6726, Testing Method for Polyvinyl Alcohol.

[0268] When the polyol-modified polysaccharide in the present disclosure is a polysaccharide obtained by modifying a polysaccharide, the degree of polymerization of the polyol-modified polysaccharide refers to the average degree of polymerization of the polysaccharide. The average degree of polymerization of a polysaccharide can be analyzed as follows. The degree of polymerization refers to the number of monosaccharide units (fructose and glucose units) in the polysaccharide. The average degree of polymerization is determined, for example, by the top of the peaks in the analysis results obtained by a conventional analytical method such as HPLC, GC, or HPAEC. The average degree of polymerization can be measured using, for example, an ULTRON PS-80N (8 × 300 mm) column manufactured by Shinwa Chemical Industry Co., Ltd. (solvent: water, flow rate: 0.5 ml / min, temperature: 50°C) or a TSK-GEL G30000 PWXL (7.8 × 300 mm) column manufactured by Tosoh Corporation (solvent: water, flow rate: 0.5 ml / min, temperature: 50°C) and a differential refractometer as a detector.

[0269] The modified polyol may be low molecular weight (eg, weight average molecular weight less than 1500, less than 1000, 500 or less) and / or high molecular weight. The weight average molecular weight of the polyol-modified product may be 100 or more, 200 or more, 300 or more, 400 or more, 500 or more, 1000 or more, 3000 or more, 5000 or more, 10,000 or more, 30,000 or more, 100,000 or more, 300,000 or more, or 500,000 or more; or may be 1,000,000 or less, 750,000 or less, 500,000 or less, 300,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, 9,000 or less, 8,000 or less, 7,000 or less, 6,000 or less, 5,000 or less, 3,000 or less, 2,000 or less, 1,000 or less, or 500 or less.

[0270] The substitution rate of hydroxy groups in the polyol-modified product may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 100%, 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 be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, 15% or less, for example 95% or less. Here, the "substitution rate" refers to the proportion (mol%) of hydroxy groups derived from the polyol that are modified, and may refer to the proportion (mol%) that are modified with optionally substituted monovalent hydrocarbon groups having 6 to 40 carbon atoms or monovalent polysiloxane groups.

[0271] The residual hydroxyl group ratio in the polyol-modified product may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, for example, 5% or more, 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, the "residual ratio" refers to the proportion (mol%) of unmodified hydroxyl groups derived from the polyol.

[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 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 from 6 to 40 carbon atoms or a monovalent polysiloxane group, which may have a substituent.

[0273] The modifying group equivalent of the polyol modified product may be 150 or more, 250 or more, 350 or more, 450 or more, 550 or more, 650 or more, 750 or more, or 1000 or more, and may be 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, or 400 or less. This is the value obtained by dividing the weight-average molecular weight of the polyol modified product by the number of modifying groups. Here, the modifying group is preferably a monovalent hydrocarbon group having 6 to 40 carbon atoms or a monovalent polysiloxane group, which may have a substituent.

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

[0275] For details about the monovalent hydrocarbon group having 6 to 40 carbon atoms and the monovalent polysiloxane group, which may have a substituent, the above descriptions of (the hydrocarbon group having 6 or more carbon atoms and which may have a substituent) and (the polysiloxane group) are incorporated herein by reference.

[0276] (-Y O -Z O n ) In the present disclosure, modified polyols are those in which one or more hydroxy groups of the polyol have the formula: -Y O -Z O n [In the formula, Y O is Y O1 and Y O2 is a (1+n) valent group consisting of one or more members selected from the group consisting of Y O1is a group consisting of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2, and -N(-)2 (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms)), Y O2 is a group consisting of one or more members selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent hydrocarbon aromatic rings, and optionally substituted di- to tetravalent heterocycles, Z O represents a monovalent hydrocarbon group having 6 to 40 carbon atoms or a monovalent polysiloxane group which may have a substituent, n is an integer between 1 and 3. It may be substituted with a group represented by the following formula:

[0277] (Y O ) Y O is Y O1 and Y O2 is a (1+n) valent group consisting of one or more members selected from the group consisting of Y O1 is a group consisting of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2, and -N(-)2 (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms)), Y O2 is a group composed of one or more members selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent hydrocarbon aromatic rings, and optionally substituted di- to tetravalent heterocycles.

[0278] n is Y O Z combines withO and may be an integer of 1 or more and 3 or less. n may be 1 or more, 2 or more, or 3 or more, or 3 or less, 2 or less, or 1 or less, for example, 2 or less.

[0279] Y O The molecular weight of 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 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 may contain at least an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfonamide group, a sulfoneurea group, a sulfoneurethane group, or a sulfonimide group. O may include -C(=O)-NR'-, -C(=S)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SONR'-. O By including these groups, the liquid repellency can be improved.

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

[0282] Y O1 is a direct bond or a divalent or higher valent group. O1 The valence of Y may be 2 to 4, 2 to 3, or 2. O1 is preferably not only a direct bond.

[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 may be one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -S(=O)2-, -NR'-, -C(OR')R'-, and -C(OR')(-)2 (wherein R', in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms)). Y O1 Examples include: direct binding, -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, —C(═O)—NR′—, -SO2-, -SO2NR'-, -C(OR')R'-, -C(OR')(-)2 etc. (In the formula, R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).) Examples include:

[0285] Y O1 may contain at least an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfonamide group, a sulfoneurea group, a sulfoneurethane group, or a sulfonimide group. O2 may include -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO2NR'-. O1 By including these groups, the liquid repellency can be improved.

[0286] ○ Y O2 Y O2 is a linker of a hydrocarbon ring which may have a substituent, a hydrocarbon aromatic ring which may have a substituent, or a heterocyclic ring which may have a substituent.

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

[0288] Y O2 is a divalent or higher valent group. O2 The valence of may be, for example, 2 to 4, 2 to 3, or 2.

[0289] Y O2 may have 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 carbon atoms, 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 is composed of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent hydrocarbon aromatic rings, and optionally substituted di- to tetravalent heterocycles.

[0291] The di- to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or straight-chain hydrocarbon group. The di- to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group having 1 to 40 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more, and may be 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less. The valence of the aliphatic hydrocarbon group may be 2 or more, 3 or more, or 4 or less, 4 or less, 3 or less, or 2.

[0292] The aliphatic hydrocarbon group may have a substituent. Examples of the substituent include -OR', -N(R')2, -COOR', and a halogen atom (wherein R', in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have an active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the substituted aliphatic hydrocarbon group, the 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.

[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-constituting atoms of the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12, and preferably 5 to 12. The valence of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0294] The hydrocarbon aromatic ring may have a substituent. Examples of the substituent include -R', -OR', -N(R')2, -COOR', and a halogen atom (wherein R', in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have an active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the substituted hydrocarbon aromatic ring, the ratio of carbon atoms to the total 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 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

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

[0296] The heterocycle may have a substituent. Examples of the substituent include -R', -OR', -N(R')2, -COOR', and a halogen atom (wherein R', in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have an active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the substituted heterocycle, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, for example, 65 mol% or more, 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.] etc.

[0298] Y O2 Specific examples include: -(CH2) p - (p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and having an unsaturated bond; a hydrocarbon group having a branched structure and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms; -(CH2) q -Cy-(CH2) r -(q and r each independently represent a number from 0 to 20, for example, 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle). etc.

[0299] (Y O (Example) Y O In the following, R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20, 1 to 10, or 1 to 4 carbon atoms).

[0300] Y O An example of this is Y O If is bivalent, -Y O1 -, -Y O1 -Y O2 -, -Y O1 -Y O2 -Y O1 -, -Y O1 -Y O2 -Y O1 -Y O2 -, -Y O2 -, -Y O2 -Y O1 -, -Y O2 -Y O1 -Y O2 -, -Y O2 -Y O1 -Y O2 -Y O1 -etc.

[0301] Y O An example of this is Y O If 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 -) 2、 -Y O2 -Y O1 -(Y O2 -Y O1 -) 2、 -Y O2 -(Y O1 -Y O2 -Y O1 -)2 etc. can be mentioned.

[0302] Y O As an example of Y O when it is tetravalent, -Y O1 (-)3, -Y O1 -Y O2 (-)3, -Y O1 -(YO2 -), 3, -Y O1 -Y O2 -Y O1 (-), 3, -Y O1 -Y O2 (-Y O1 (-), 3, -Y O1 -(Y O2 -Y O1 (-), 3, -Y O1 -Y O2 -Y O1 -Y O2 (-), 3, -Y O1 -Y O2 -Y O1 -(Y O2 -), 3、 -Y O1 -Y O2 -(Y O1 -Y O2 -), 3、 -Y O1 -(Y O2 -Y O1 -Y O2 -), 3; -Y O2 (-), 3, -Y O2 -Y O1 (-), 3, -Y O2 -(Y O1 (-), 3, -Y O2 -Y O1 -Y O2 (-), 3, -Y O2 -Y O1 (-Y O2 (-), 3, -Y O2 -(Y O1 -Y O2 (-), 3, -Y O2 -Y O1 -Y O2 -Y O1 (-), 3, -Y O2 -Y O1 -Y O2 -(Y O1 -), 3、 -Y O2 -Y O1 -(Y O2 -Y O1 -), 3、 -Y O2 -(Y O1 -Y O2 -Y O1 -), 3; etc. 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.

[0304] (Preferred Y O (Example) Preferably, Y O but -OY O11 -or -OY O11 -Y O21 -Y O12 - wherein each symbol represents independently at each occurrence: Y O11 is a direct bond, —C(═O)—, —C(═O)—NR′—, or —C(═S)—NR′—; Y O21 is a hydrocarbon group having 1 to 40 carbon atoms, Y O12 is -O-, -OC(=O)-, -OC(=O)-O-, -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO2-, -SON2NR'-, -C(OR')R'-, or -C(OR')(-)2; It may be.

[0305] Y O11is a non-hydrocarbon linker, which is a direct bond or a divalent or higher 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 be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

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

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

[0309] Y O21 may have 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 carbon atoms, 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.

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

[0311] Y O21 Specific examples include: -(CH2) p - (p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and having an unsaturated bond; a hydrocarbon group having a branched structure and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms; -(CH2) q -Cy-(CH2) r -(q and r each independently represent a number from 0 to 20, for example, 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle). etc.

[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)—O—, —C(═O)—NR′—, —SO—, —SONR′—, —C(OR′)R′—, or —C(OR′)(−)2.

[0313] Y O12 may contain at least an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfonamide group, a sulfoneurea group, a sulfoneurethane group, or a sulfonimide group. O12 may be -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO2NR'-. C12 By including these groups, the liquid repellency can be improved.

[0314] (Z O ) Z O represents a monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, or a monovalent polysiloxane group, and the above explanations for (the hydrocarbon group having 6 or more carbon atoms which may have a substituent) and (the polysiloxane group) are incorporated herein by reference.

[0315] [Other modifying groups] The hydroxy group of the polyol is -Y O -Z O n The group may be substituted with a modifying group other than the following: Examples of the modifying group are anionic groups and / or cationic groups.

[0316] Examples of the anionic group include a monomer having a carboxyl group, a sulfonic acid group, or a phosphoric acid group.

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

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

[0319] The cationic group in the form of a salt is a salt with an acid (organic acid or inorganic acid). Organic acids, such as carboxylic acids having 1 to 20 carbon atoms (particularly monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and stearic acid) are preferred.

[0320] [Manufacturing method] The modified polyol may be prepared by reacting a modifying agent having a modifying group (or a precursor structure of the modifying group) with the hydroxy group of the polyol.

[0321] (Polyol) A polyol is a compound having two or more hydroxy groups and is a compound that serves as a raw material for a modified polyol. A polyol is a compound having two or more hydroxy groups in the molecule. The polyol may be aliphatic or aromatic, but is preferably aliphatic.

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

[0323] When the polyol is a polymer, the repeating structure of the monomer unit may contain a hydroxy group and an ether bond.

[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, 10,000 or more, 30,000 or more, 100,000 or more, 300,000 or more, or 500,000 or more; or 1,000,000 or less, 750,000 or less, 500,000 or less, 300,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, 5000 or less, 300,000 or less, 2,000 or less, 1,000 or less, or 500 or less.

[0325] The number of hydroxy groups in the polyol may be 2 or more, 5 or more, 7 or more, 10 or more, 15 or more, 30 or more, 50 or more, or 100 or more, and may be 3000 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less.

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

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

[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 catechin, quercetin, and anthocyanin.

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

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

[0338] An example of a polyether polyol may be a compound obtained by addition polymerization of an alkylene oxide to an initiator. Examples of initiators include compounds having two or more functional hydroxyl groups. Examples of initiators include propylene glycol, polypropylene glycol, ethylene glycol, polyethylene glycol, glycerin, polyglycerin, trimethylolpropane, triethanolamine, pentaerythritol, ethylenediamine, aromatic diamines, diethylenetriamine, sorbitol, and sucrose. Examples of alkylene oxides include ethylene oxide and propylene oxide. Polyether polyols obtained by addition polymerization of alkylene oxide to the above initiators are also referred to as polyoxyalkylene polyols or oxyalkylene derivatives of polyols. Representative examples of polyether polyols include polyoxypropylene triol, obtained by addition polymerization of propylene oxide to glycerin, and polyoxypropylene polyglyceryl ether, obtained by addition polymerization of propylene oxide to polyglycerin.

[0339] An example of a polymer polyol is a compound obtained by polymerizing at least a portion of a polyether polyol with an ethylenically unsaturated monomer, such as acrylonitrile or styrene.

[0340] Examples of polyester polyols include compounds obtained by dehydration condensation of a compound having two or more functional carboxyl groups with a compound having two or more functional hydroxyl groups. Examples of compounds having two or more functional carboxyl groups include terephthalic acid, isophthalic acid, phthalic acid, methylphthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, succinic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, and acid anhydrides thereof. Examples of compounds having two or more functional hydroxyl groups include ethylene glycol, propylene glycol, propanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and polymers thereof.

[0341] (modifying agent) The modifying agent is preferably a compound that is reactive with polyol and has the above-mentioned monovalent hydrocarbon group having 6 to 40 carbon atoms or a monovalent polysiloxane group, which may have a substituent.

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

[0343] Z in the structure of the above modifier O may be replaced with any group constituting the modifying group, for example, Z O may be a group having a monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent or a monovalent polysiloxane group, or, for example, Z O A-Y O -Z O n It may also be possible to use the following.

[0344] A modified polyol may be synthesized by reacting a polyol with a modifying agent. For example, a modified polyol can be synthesized by reacting a modifying agent such as an acid halide compound, an acid anhydride, or a carboxylic acid with a hydroxy group of a polyol to form an ester bond. Alternatively, a modified polyol can be produced by reacting a modifying agent such as a halide or an epoxy compound with a hydroxy group of a polyol to form an ether bond. Those skilled in the art can appropriately design the reaction conditions between a polyol and a modifying agent, such as by using a catalyst (e.g., an acid catalyst or a base catalyst) or a condensing agent, depending on the desired product.

[0345] [Polycarboxylic acid modified product] As an example of the liquid-repellent compound, a modified polycarboxylic acid will be described. The modified polycarboxylic acid is a compound obtained by chemically modifying a polycarboxylic acid so as to exhibit liquid-repellent properties.

[0346] [Structure etc.] The polycarboxylic acid modification may be low molecular weight (eg, weight average molecular weight less than 1500, less than 1000, 500 or less) and / or high molecular weight. The weight average molecular weight of the polycarboxylic acid modified product may be 100 or more, 200 or more, 300 or more, 400 or more, 500 or more, 1000 or more, 3000 or more, 5000 or more, 10,000 or more, 30,000 or more, 100,000 or more, 300,000 or more, or 500,000 or more; or may be 1,000,000 or less, 750,000 or less, 500,000 or less, 300,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, 9,000 or less, 8,000 or less, 7,000 or less, 6,000 or less, 5,000 or less, 3,000 or less, 2,000 or less, 1,000 or less, or 500 or less.

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

[0348] The weight average molecular weight (Mw), number average molecular weight (Mn) and polydispersity index (Mw / Mn) of the polycarboxylic acid modified product, calculated as polystyrene, may be determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an eluent and Shodex KF400RL and KF400RH columns (polystyrene gel) manufactured by Showa Denko K.K.

[0349] The substitution rate of hydroxy groups for carboxyl groups in the modified polycarboxylic acid may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 100%, and is preferably 10% or more, for example, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, particularly 80% or more, and may be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, 15% or less, for example, 95% or less. Here, the "substitution rate" refers to the proportion (mol %) of hydroxy groups of carboxyl groups derived from polycarboxylic acid that are modified, and may refer to the proportion (mol %) that are modified with monovalent hydrocarbon groups having 6 to 40 carbon atoms or monovalent polysiloxane groups that may have a substituent.

[0350] The residual hydroxyl group ratio of carboxyl groups in the modified polycarboxylic acid may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, for example, 5% or more, and may be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, 15% or less, or 5% or less, for example, 50% or less, 30% or less, or 10% or less. Here, the "residual ratio" refers to the proportion (mol %) of unmodified hydroxyl groups in carboxyl groups derived from the polycarboxylic acid.

[0351] The number of modifying groups possessed by the polycarboxylic acid modified product may be 2 or more, 5 or more, 7 or more, 10 or more, 15 or more, 30 or more, or 50 or more, and may be 1000 or less, 750 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less. Here, the modifying group is preferably a monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent, or a monovalent polysiloxane group.

[0352] The modifying group equivalent of the polycarboxylic acid modified product may be 150 or more, 250 or more, 350 or more, 450 or more, 550 or more, 650 or more, 750 or more, or 1000 or more, and may be 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, or 400 or less. This is the value obtained by dividing the weight-average molecular weight of the polycarboxylic acid modified product by the number of modifying groups. Here, the modifying group is preferably a monovalent hydrocarbon group having 6 to 40 carbon atoms or a monovalent polysiloxane group, which may have a substituent.

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

[0354] For details about the monovalent hydrocarbon group having 6 to 40 carbon atoms and the monovalent polysiloxane group, which may have a substituent, the above descriptions of (the hydrocarbon group having 6 or more carbon atoms and which may have a substituent) and (the polysiloxane group) are incorporated herein by reference.

[0355] (-Y C -Z C n ) In the present disclosure, the modified polycarboxylic acid is a polycarboxylic acid in which the hydroxy group of one or more carboxyl groups has the following formula: -Y C -Z C n [In the formula, Y C is Y C1 and Y C2 is a (1+n) valent group consisting of one or more members selected from the group consisting of Y C1is a group consisting of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2, and -N(-)2 (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms)), Y C2 is a group consisting of one or more members selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent hydrocarbon aromatic rings, and optionally substituted di- to tetravalent heterocycles, Z C represents a monovalent hydrocarbon group having 6 to 40 carbon atoms or a monovalent polysiloxane group which may have a substituent, n is an integer between 1 and 3. It may be substituted with a group represented by the following formula:

[0356] (Y C ) Y C is Y C1 and Y C2 is a (1+n) valent group consisting of one or more members selected from the group consisting of Y C1 is a group consisting of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2, and -N(-)2 (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms)), Y C2 is a group composed of one or more members selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent hydrocarbon aromatic rings, and optionally substituted di- to tetravalent heterocycles.

[0357] n is Y C Z combines withC and may be an integer of 1 or more and 3 or less. n may be 1 or more, 2 or more, or 3 or more. n may be 3 or less, 2 or less, or 1 or less, for example, 2 or less.

[0358] Y C The molecular weight of 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 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 may contain at least an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfonamide group, a sulfoneurea group, a sulfoneurethane group, or a sulfonimide group. C may be -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO2NR'-. C By including these groups, the liquid repellency can be improved.

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

[0361] Y C1 is a direct bond or a divalent or higher valent group. C1 The valence of Y may be 2 to 4, 2 to 3, or 2. C1 is preferably not only a direct bond.

[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 be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0363] Y C1may be one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -S(=O)2-, -NR'-, -C(OR')R'-, and -C(OR')(-)2 (wherein R', in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms)). Y C1 Examples include: direct binding, -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, —C(═O)—NR′—, -SO2-, -SO2NR'-, -C(OR')R'-, -C(OR')(-)2 etc. (In the formula, R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).) Examples include:

[0364] Y C1 may contain at least an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfonamide group, a sulfoneurea group, a sulfoneurethane group, or a sulfonimide group. C1 may include -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO2NR'-. C1 By including these groups, the liquid repellency can be improved.

[0365] ○ Y C2 YC2 is a linker of a hydrocarbon ring which may have a substituent, a hydrocarbon aromatic ring which may have a substituent, or a heterocyclic ring which may have a substituent.

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

[0367] Y C2 is a divalent or higher valent group. C2 The valence of may be, for example, 2 to 4, 2 to 3, or 2.

[0368] Y C2 may have 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 carbon atoms, 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.

[0369] Y C2 is composed of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent hydrocarbon aromatic rings, and optionally substituted di- to tetravalent heterocycles.

[0370] The di- to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or straight-chain hydrocarbon group. The di- to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group having 1 to 40 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more, and may be 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less. The valence of the aliphatic hydrocarbon group may be 2 or more, 3 or more, or 4 or less, 4 or less, 3 or less, or 2.

[0371] The aliphatic hydrocarbon group may have a substituent. Examples of the substituent include -OR', -N(R')2, -COOR', and a halogen atom (wherein R', in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have an active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the substituted aliphatic hydrocarbon group, the 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.

[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-constituting atoms of the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12, and preferably 5 to 12. The valence of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0373] The hydrocarbon aromatic ring may have a substituent. Examples of the substituent include -R', -OR', -N(R')2, -COOR', and a halogen atom (wherein R', in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have an active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the substituted hydrocarbon aromatic ring, the 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.

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

[0375] The heterocycle may have a substituent. Examples of the substituent include -R', -OR', -N(R')2, -COOR', and a halogen atom (wherein R', in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have an active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the substituted heterocycle, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, for example, 65 mol% or more, and 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.] etc.

[0377] Y C2 Specific examples include: -(CH2) p - (p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and having an unsaturated bond; a hydrocarbon group having a branched structure and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms; -(CH2) q -Cy-(CH2) r -(q and r each independently represent a number from 0 to 20, for example, 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle). etc.

[0378] (Y C (Example) Y C In the following, R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20, 1 to 10, or 1 to 4 carbon atoms).

[0379] Y C An example of this is Y C If is bivalent, -Y C1 -, -Y C1 -Y C2 -, -Y C1 -Y C2 -Y C1 -, -Y C1 -Y C2 -Y C1 -Y C2 -, -Y C2 -, -Y C2 -Y C1 -, -Y C2 -Y C1 -Y C2 -, -Y C2 -Y C1 -Y C2 -Y C1 -etc.

[0380] Y C An example of this is Y C If is trivalent, -Y C1 (-)2, -Y C1 -Y C2 (-)2, -Y C1 -(Y C2 -)2, -Y C1 -Y C2 -Y C1 (-)2, -Y C1 -Y C2 (-Y C1 -)2, -Y C1 -(Y C2 -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']](-)2, -Y C2 -Y C1 (-)2, -Y C2 -(Y C1 (-)2, -Y C2 -Y C1 -Y C2 (-)2, -Y C2 -Y C1 (-Y C2 (-)2, -Y C2 -(Y C1 -Y C2 (-)2, -Y C2 -Y C1 -Y C2 -Y C1 (-)2, -Y C2 -Y C1 -Y C2 -(Y C1 -) 2、 -Y C2 -Y C1 -(Y C2 -Y C1 -) 2、 -Y C2 -(Y C1 -Y C2 -Y C1 Examples such as -)2 etc. can be mentioned.

[0381] Y C As an example of Y C when Y 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 Preferred examples of -Y C1 -, -Y C1 -Y C2 -, -Y C1 -Y C2 -Y C1 -, -Y C1 -Y C2 (-)2, -Y C2 -, -Y C2 -Y C1 -, -Y C2 -Y C1 -Y C2 -, -Y C2 -Y C1 (-)2, etc.

[0383] (Preferred Y C (Example) Preferably, Y C but -Y C11 -or -Y C11 -Y C21 -Y C12 - wherein each symbol represents independently at each occurrence: Y C11 is -O- or -NR'-, Y C21 is a hydrocarbon group having 1 to 40 carbon atoms, Y C12 is -O-, -OC(=O)-, -OC(=O)-O-, -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO2-, -SON2NR'-, -C(OR')R'-, or -C(OR')(-)2; It may be.

[0384] Y C11 is a non-hydrocarbon linker, which is a direct bond or a divalent or higher 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 be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

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

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

[0388] Y C21 may have 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 carbon atoms, 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.

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

[0390] Y C21 Specific examples include: -(CH2) p - (p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and having an unsaturated bond; a hydrocarbon group having a branched structure and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms; -(CH2) q -Cy-(CH2) r -(q and r each independently represent a number from 0 to 20, for example, 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle). etc.

[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)—O—, —C(═O)—NR′—, —SO—, —SONR′—, —C(OR′)R′—, or —C(OR′)(−)2.

[0392] Y C12 may contain at least an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfonamide group, a sulfoneurea group, a sulfoneurethane group, or a sulfonimide group. C12 may be -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO2NR'-. C12 By including these groups, the liquid repellency can be improved.

[0393] (Z C ) Z C represents a monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, or a monovalent polysiloxane group, and the above explanations for (the hydrocarbon group having 6 or more carbon atoms which may have a substituent) and (the polysiloxane group) are incorporated herein by reference.

[0394] [Other modifying groups] The hydroxy group of the polycarboxylic acid is -Y C -Z C n The polyol may be substituted with a modifying group other than the above. Examples of the modifying group are anionic groups and / or cationic groups. The above-mentioned explanation of [Other modifying groups] in the polyol is applicable to the anionic group and / or cationic group.

[0395] [Manufacturing method] The modified polycarboxylic acid may be prepared by reacting a modifying agent having a modifying group (or a precursor structure of the modifying group) with the hydroxy group of the polycarboxylic acid.

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

[0397] The polycarboxylic acid 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 polycarboxylic acid may be 100 or more, 300 or more, 500 or more, 1000 or more, 3000 or more, 5000 or more, 10,000 or more, 30,000 or more, 100,000 or more, 300,000 or more, or 500,000 or more; or 1,000,000 or less, 7,500,000 or less, 500,000 or less, 3,000,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, 5000 or less, 3,000 or less, 2,000 or less, 1,000 or less, or 500 or less.

[0398] The number of carboxyl groups in the polycarboxylic acid may be 2 or more, 5 or more, 7 or more, 10 or more, 15 or more, 30 or more, 50 or more, or 100 or more, and may be 3000 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less.

[0399] The carboxyl group equivalent of the polycarboxylic acid may be 20 or more, 40 or more, 60 or more, 80 or more, 100 or more, 120 or more, or 150 or more, and may be 1000 or less, 800 or less, 600 or less, 400 or less, 200 or less, 100 or less, or 75 or less. The carboxyl equivalent of the polycarboxylic acid is the value obtained by dividing the weight average molecular weight of the polycarboxylic acid by the number of hydroxyl groups.

[0400] The polycarboxylic acid may be a natural product. The natural product may be a high molecular weight natural product, a low molecular weight natural product, or a derivative thereof. The natural product also includes compounds converted from microorganisms.

[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, such as oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, phthalic acid, terephthalic acid, malic acid, tartaric acid, aldaric acid, and salts thereof.

[0403] Tricarboxylic acids are compounds having three carboxyl groups, and examples thereof include citric acid, tricarballylic acid, t-aconitic acid, trimellitic acid, and salts thereof.

[0404] Tetracarboxylic acids are compounds having four carboxyl groups, and examples thereof include pyromellitic acid and salts thereof.

[0405] The carboxyl group-containing compound polymer is a compound having five or more carboxyl groups, and examples thereof include alginic acid, tragacanth gum, gum arabic, polyacrylic acid, polymethacrylic acid, polymaleic acid, polyaspartic acid, polyglutamic acid, hyaluronic acid, heparin, xanthan gum, gellan gum, carboxymethylcellulose alginate, galacturonic acid, mannuronic acid, and salts thereof.

[0406] (modifying agent) The modifying agent is preferably a compound that is reactive with polycarboxylic acid and has the above-mentioned monovalent hydrocarbon group having 6 to 40 carbon atoms or a monovalent polysiloxane group, which may have a substituent.

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

[0408] Z in the structure of the above modifier C may be replaced with any group constituting the modifying group, for example, Z C may be a monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, or may be, for example, Z C A-Y C -Z C n It may also be possible to use the following.

[0409] The modified polycarboxylic acid may be synthesized by reacting a polycarboxylic acid with a modifying agent. For example, the modifying agent, which is an epoxy compound, may be reacted with the carboxyl group of the polycarboxylic acid to form an ester bond, thereby producing the modified polycarboxylic acid. Those skilled in the art can appropriately design the reaction conditions between the polycarboxylic acid and the modifying agent, such as by using a catalyst (e.g., an acid catalyst or a base catalyst) or a condensing agent, depending on the desired product.

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

[0411] The waxes of the present disclosure can be adhered to a substrate (particularly a pulp substrate) to impart liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or stain resistance, to the substrate.

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

[0413] The wax may be in a particulate (powder) form. The average particle size of the wax may be 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.2 μm or more, 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, or 0.6 μm or more, or 10 μm or less, 5 μm or less, 3 μm or less, 1 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, 0.3 μm or less, or 0.2 μm or less, preferably 1 μm or less. The above particle size is the primary particle size. A particle size within the above range can provide excellent particle stability and good liquid repellency. The average particle size can be measured using a microscope (scanning electron microscope). Specifically, a wax particle sample is observed under a microscope at an arbitrary magnification. Next, if the particle shape is spherical, the diameter is considered to be the particle size, and if it is non-spherical, the average of the longest and shortest diameters is considered to be the particle size. By measuring the particle size of all particles present within the field of view, then moving the field of view and measuring the particle size again, the particle size is measured at 100 or more points, and the average value is considered to be 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 be 100° or less, 90° or less, or 75° or less. When the wax has an HD contact angle equal to or greater than the above lower limit, it can impart good liquid repellency (especially oil repellency) to the substrate. The HD contact angle is the static contact angle of the wax with a spin-coated film, and is obtained by dropping 2 μL of HD onto the spin-coated film and measuring the contact angle 1 second after the drop lands.

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

[0416] The wax may be a low molecular weight (for example, a molecular weight of 1000 or less, or 500 or less) or a polymer. When the wax is a polymer, its weight average molecular weight may be 1000 or more, 3000 or more, 5000 or more, 7500 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more, or may be 10000000 or less, 75000000 or less, 50000000 or less, 3000000 or less, 1000000 or less, 750000 or less, 500000 or less, 300000 or less, 1 ... or less, 50000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 100000 or less, 75000 or less, 50

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

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

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

[0420] The isocyanate derivative is a compound obtained by reacting an active hydrogen compound with a raw material isocyanate, and has a portion derived from the active hydrogen-containing compound and a portion derived from the raw material isocyanate. Unlike isocyanate-based curing agents, the isocyanate derivative does not usually have an isocyanate group.

[0421] The isocyanate derivative has -NHCO- formed by the reaction of an active hydrogen compound with a starting isocyanate (where -NHCO- may be part of a urethane group or a urea group). -NHCO- is a group formed by the reaction of an active hydrogen-containing group (typically a hydroxy group) of the active hydrogen compound with an active hydrogen-reactive group (typically an isocyanate group) of the starting isocyanate. The isocyanate derivative is typically a urethane (particularly a polyurethane).

[0422] The hydrocarbon group having 6 to 40 carbon atoms in the isocyanate derivative is preferably a monovalent hydrocarbon group. For the hydrocarbon group having 6 to 40 carbon atoms, the above explanation (hydrocarbon group having 6 or more carbon atoms which may have a substituent) is applicable.

[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, and is 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 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 3,000 or more, 5,000 or more, 10,000 or more, 30,000 or more, 100,000 or more, 300,000 or more, or 500,000 or more, and may be 1,000,000 or less, 750,000 or less, 500,000 or less, 300,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, or 5,000 or less.

[0425] [Active hydrogen compounds] The active hydrogen compound contains an active hydrogen group that reacts with an isocyanate group.

[0426] Examples of the active hydrogen group include a hydroxy group, an amino group, and a carboxyl group, and a typical example is a hydroxy 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 the aforementioned hydrocarbon group having 6 to 40 carbon atoms, and the above description is incorporated herein.

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

[0430] Examples of the active hydrogen compound (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 isomyristyl alcohol, isocetyl alcohol, isostearyl alcohol, and isoicosyl alcohol; linear unsaturated hydrocarbon group-containing alcohols such as tetradecenyl alcohol, hexadecenyl alcohol, oleyl alcohol, icosenyl alcohol, docosenyl alcohol, tetracosenyl alcohol, hexacosenyl alcohol, and octacosenyl 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, and 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 for example, 90 parts by mass or less, preferably 80 parts by mass or less, relative to 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 for example, 60 parts by mass or less, preferably 45 parts by mass or less, more preferably 30 parts by mass or less, relative to 100 parts by mass of the total amount of the linear saturated hydrocarbon group-containing alcohol and the linear unsaturated hydrocarbon group-containing alcohol. When the blending ratio of the linear saturated hydrocarbon group-containing alcohol is equal to or greater than the lower limit, the crystallinity of the hydrocarbon group is improved, and as a result, the liquid repellency of the object treated with this repellent can be improved.

[0432] (α2) sugar alcohol / hydroxy acid modified The active hydrogen compound may be a modified sugar alcohol / hydroxy acid (α2), which is a sugar alcohol / hydroxy acid (sugar alcohol and / or hydroxy acid) in which a hydrocarbon group having 6 to 40 carbon atoms has been modified. 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, and examples of hydroxy acids include hydroxy polycarboxylic acids. The sugar alcohol / hydroxy acid may be a substance present in a living body. Examples of sugar alcohols / hydroxy acids include, but are not limited to, compounds derived from aldoses and ketoses, such as tetroses, pentoses, hexoses, and heptoses, and specific examples include glucose, glyceraldehyde, erythrose, arabinose, ribose, arabinose, allose, altrose, mannose, xylose, lyxose, gulose, galactose, talose, fructose, ribulose, mannoheptulose, sedoheptulose, threose, erythritol, threitol, glucopyranose, mannopyranose, and the like. Examples of suitable sugar alcohols / hydroxy acids include talopyranose, allopyranose, altropyranose, idopyranose, gulopyranose, glucitol, mannitol, erythritol, sorbitol, arabitol, xylitol, ribitol, galactitol, fucitol, iditol, inositol, pentaerythritol, dipentaerythritol, volemitol, gluconic acid, glyceric acid, xylonic acid, galactaric acid, ascorbic acid, citric acid, gluconic acid lactone, glyceric acid lactone, xylonic acid lactone, glucosamine, galactosamine, and 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 30 or less, 20 or less, or 10 or less. The average OH value of compound (α2) may be in the range of more than 0 to about 230, preferably about 10 to about 175, and 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 compound (α2) may be 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more, and may be 12 or less, 9 or less, 6 or less, or 3 or less.

[0434] In the sugar alcohol / hydroxy acid modified compound (α2), at least one active hydrogen atom (e.g., an OH group, a hydrogen atom in a carboxyl group) of the sugar alcohol and / or the 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 or mixtures thereof, wherein R α2 is a hydrogen atom or a hydrocarbon group having from 6 to 40 carbon atoms, 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 (one or more) of the active hydrogens of the sugar alcohol / hydroxy acid may be unmodified, and the active hydrogen (e.g., an -OH group) may react with an active hydrogen reactive group (particularly an isocyanate group) of compound (b) to form -NHCO-.

[0435] (α21) Sorbitan modified 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. The sorbitan may be modified by -R α2 , -C(O)R α2 , -(CH2CH2O) n (CH(CH3)CH2O) m R α2 , -(CH2CH2O) n (CH(CH3)CH2O) m C(O)R α2or a mixture thereof (wherein R α2 is a hydrocarbon group with 6 to 40 carbon atoms. For example, sorbitan is -C(O)R α2 The alkyl sorbitan may be a mono-, di-, or tri-substituted compound. Here, the sorbitan may contain an amount of sorbitol, isosorbide, or other intermediates or by-products. Commercially available sorbitans such as SPAN can be used as the alkyl sorbitan.

[0436] In one embodiment, at least one active hydrogen substituent is —C(O)R α2 R may be α2 may be a straight-chain or branched-chain alkyl group having 6 to 40 carbon atoms, more preferably 7 to 21, and most preferably 11 to 21. Preferred compounds include mono-, di-, and tri-substituted sorbitans derived from caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, and mixtures thereof. Particularly preferred compounds include mono-, di-, and tri-substituted sorbitan stearates or sorbitan behenin.

[0437] In one embodiment, R α2 may contain at least one unsaturated bond. Examples of such compounds (wherein at least one active hydrogen substituent is -C(O)R α2 Selected from R α2 contains at least one unsaturated bond), sorbitan trioleate (i.e., in which R α2 Ha-C7H 14 CH=CHC8H 17 Other examples include, but are not limited to, mono-, di-, and tri-substituted sorbitans derived from palmitoleic acid, linoleic acid, arachidonic acid, and erucic acid.

[0438] In one aspect, the sorbitan modification (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 (wherein each m is independently 0 to 20, each n is independently 0 to 20, and m+n is greater than 0). Such compounds are known as polysorbates and are commercially available under the trade name TWEEN. These sorbitans are also known as R α2 Commercially available polysorbates can be mono-, di-, or trisubstituted with each R 2 From various polysorbates where R is H (unsubstituted), α2 It is known that sorbitan modifications (α21) contain a wide variety of mixtures ranging from polysorbates in which m is a linear or branched alkyl group having 6 to 40 carbon atoms (fully substituted), and mixtures of these various substitutions. Examples of such sorbitan modifications (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 trioleate (where R α2 is C7H 14 CH=CHC8H 17 and is commercially available under the name Polysorbate 80. Sorbitan modifications (α21) may include mixtures of compounds with various active hydrogen substituents, and R α2 a compound in which R contains at least one unsaturated bond; α2 may include mixtures with fully saturated compounds.

[0439] (α22) citrate modified The sugar alcohol / hydroxy acid modification (α2) may be a citric acid modification (α22) in which citric acid is modified with a hydrocarbon group having 6 to 40 carbon atoms, in particular an alkyl citrate. For example, the citric acid modification (α22) may be mono-, di-, or tri-substituted with alkyl groups. Mixtures of citrates with various values of active hydrogen substituents may also be used, and R α2 a compound having a hydrocarbon group having at least one unsaturated bond, and R α2 The citric acid modification (α22) may contain a mixture of -(CH2CH2O) and a compound in which -(CH2CH2O) is a fully saturated hydrocarbon. n (CH(CH3)CH2O) m R α2 or -(CH2CH2O) n (CH(CH3)CH2O) m C(O)R α2 wherein R α2 is a hydrocarbon group having 6 to 40 carbon atoms.) Examples of citric acid modifications (α22) include, but are not limited to, trialkyl citrates.

[0440] (α23) Pentaerythritol modified 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, or may be a mono-, di-, or tri-substituted product having a hydrocarbon group (particularly an alkyl group) having 6 to 40 carbon atoms, such as a dipentaerythriol ester. The active hydrogen substituent is -CH2C[CH2OR α2 ]3 (wherein R α2 is a hydrocarbon group having 6 to 40 carbon atoms). The pentaerythritol modification (α23) is a compound having a mixture of hydrocarbon groups with different chain lengths, or R α2 a compound in which R contains at least one unsaturated bond; α2 The carboxylic acid may contain a mixture of fully saturated compounds with the carboxylic acid.

[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] The cationic active hydrogen compound (α3) preferably has two or more hydroxy groups per molecule.

[0443] An example of the cationic group is a tertiary amino group.

[0444] That is, 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 in a liquid medium (e.g., water) and can also introduce cationic groups that have affinity for textile products (described later) into the resin, thereby improving washing durability.

[0446] More preferably, the cationic active hydrogen compound has two hydroxyl groups per molecule as the active hydrogen groups and a tertiary amino group as the 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, and trialkanolamines such as N-triethanolamine and N-triisopropanolamine, with N-methyldiethanolamine being preferred.

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

[0449] Examples of acid compounds include organic acids and inorganic acids. Examples of organic acids include acetic acid, lactic acid, tartaric acid, malic acid, etc., preferably acetic acid and lactic acid, and more preferably acetic acid. Examples of inorganic acids include hydrochloric acid, sulfuric acid, phosphoric acid, etc., preferably hydrochloric acid. Examples of acid compounds include organic acids. When the acid compound contains an organic acid, the acid volatilizes upon heat treatment, thereby improving the liquid repellency of the treated material treated with this repellent. Furthermore, the acid volatilizes upon heat treatment, which makes it easier for cationic groups to adsorb to textile products, thereby improving the washing durability of the textile products. (α4) Other active hydrogen-containing compounds The active hydrogen compound (α) may further contain an active hydrogen compound (α4).

[0450] (α41) Compound The active hydrogen compound (α4) is represented by the formula R α41 -X α41 [In the formula, In the formula, R α41 teeth, C1-C which may contain at least one unsaturated group 30 Straight or branched alkyl, hydroxy-functional C1-C 30 Straight or branched chain alkyl, hydroxy-functional straight or branched chain C1-C 30 Polyethers, hydroxy-functional linear or branched polyesters, hydroxy-functional linear or branched organosiloxanes, thiol-functional C1-C 30 Straight or branched alkyl, amine functional C1-C 30 linear or branched alkyl, Y - R α411 R α412 R α413 N + -R α414 - (where Y is a halide ion, e.g., Cl - ), HOS(=O)2-R α414 - or R α411 R α412 C=N-(where R α411 , R α412 , Rα413 are each independently —H or C1-C6 alkyl, and R α414 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 isocyanate-reactive functional groups such as —H, where R ’ is —H or a monovalent organic group, s is an integer of 0 to 50, t is an integer of 0 to 50, and s+t is greater than 0. The compound (α41) may be represented by the following formula:

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

[0452] In one embodiment, X α41 -OH, -C(O)OH, -SH, -NH(R ’ ) and R α41 is a C1-C optionally containing at least one unsaturated group 30 Straight or branched alkyl, hydroxy-functional C1-C 30Straight or branched chain alkyl, hydroxy-functional straight or branched chain C1-C 30 Polyethers, hydroxy-functional linear or branched polyesters, hydroxy- or amine-functional linear or branched organosiloxanes, thiol-functional C1-C 30 Straight or branched alkyl, amine functional C1-C 30 It is selected from straight or branched chain alkyl.

[0453] X α41 may be —OH, and examples of such compounds (α41) include alkyl alcohols such as propanol, butanol, or fatty alcohols (R α41 C1-C optionally containing at least one unsaturated group 30 alkyl diols or polyols (R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 40 , R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 4 α41 is a hydroxyl functional group C1-C 30 alkylene glycol ethers such as alkylene glycol ethers (R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 30 , R 40 , R 51 , R 62 , R 63 , R 64 , R 65 , R 76 , R 77 , R 78 , R 79 , R 80 , R 81 , R 82 , R 83 , R 84 , R 85 , R 8 α41 is a hydroxy-functional straight or branched chain C1-C 30 Polyether), polyester polyol (R α41 is a hydroxy-functional linear or branched polyester), silicone prepolymer polyol (R α41 is a hydroxy-functional linear or branched organosiloxane), N,N-dimethylaminoethanol (R α41 is an amine functional group C1-C 30 straight or branched chain alkyl), choline chloride or betaine HCl (R α41 is Y - R α411 R α412 R α413 N + -R α414-), butanone oxime (R α41 is R α411 R α412 Examples of suitable polyether polyols include, but are not limited to, polyether polyols (where C=N-). The polyether polyols can contain only EO groups, only PO groups, only THF groups, or mixtures thereof. These polyethers can also exist as block copolymers, such as those designated by PEG-PPG-PEG (polyethylene glycol-polypropylene glycol-polyethylene glycol). The polyether glycols preferably have an average molecular weight of about 200 or greater, most preferably 350 to 2000.

[0454] X α41 may be —C(O)OH, and examples of such compounds (α41) include fatty acids (R 41) 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. α41 is a C1-C optionally containing at least one unsaturated group 30 hydroxy-containing acids (R hydroxypropyl ... α41 is a hydroxyl functional group C1-C 30 linear or branched alkyl), and mercaptoalkanoic acids such as mercaptopropionic acid (R α41 is a thiol functional group C1-C 30 and the like. The alkyl groups include, but are not limited to, straight or branched chain alkyl groups.

[0455] X α41 may be —SH, and examples of such compounds (α41) include alkyl thiols (Rα41 is a C1-C optionally containing at least one unsaturated group 30 and the like. The alkyl groups include, but are not limited to, straight or branched chain alkyl groups.

[0456] X α41 may be —NH(R′), and examples of such compounds (α41) include alkylamines (R α41 is a C1-C optionally containing at least one unsaturated group 30 Alkanolamines (R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 2 α41 is a hydroxyl functional group C1-C 30 linear or branched alkyl), silicone prepolymer polyamine (R α41 is an amine-functional linear or branched organosiloxane), alkyl diamine (R α41 is an amine functional group C1-C 30 linear or branched alkyl), and aminoalkanesulfonic acids such as 2-aminoethanesulfonic acid (R α41 is HO-S(O)2R α414 Examples of compounds include, but are not limited to,

[0457] (α42) compound Compound (α42) has the formula 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 are -H, and each independently represents -H, -R α424 , -C(O)R α424 and R α424are independently a straight-chain or branched-chain alkyl group having 5 to 29 carbon atoms which may contain at least one unsaturated bond, and z is 1 to 15.

[0458] Compound (α42) may be a 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 / caprate), decaglyceryl di(caprylate / caprate), decaglycerol, polyglycerol-3, and C18 diglyceride.

[0459] (α43) Chain extender The compound (α4) may be a chain extender (α43). The chain extender (α43) is a compound having two or more (for example, two) functional groups containing active hydrogen in the molecule. As the chain extender, known chain extenders can be used, and examples thereof include aliphatic or aromatic diols or polyols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,6-hexanediol, and cyclohexanedimethanol; aliphatic or aromatic diamines or polyamines such as ethylenediamine, piperazine, aminoethylpiperazine, phenylenediamine, and diethyltoluenediamine; phenolic hydroxyl group-containing compounds such as resorcinol, catechol, hydroquinone, bisphenol, bisphenol A, bisphenol AP (1,1-bis(4-hydroxyphenyl)-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 isocyanate] The fluorine-containing compound has a moiety derived from the starting isocyanate.

[0461] Examples of raw material isocyanates include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or a mixture thereof) (TDI), phenylene diisocyanate (m-, p-phenylene diisocyanate or a mixture thereof, 4,4'-diphenyl diisocyanate, diphenylmethane diisocyanate (4,4'-, 2,4', or 2,2'-diphenylmethane diisocyanate or a mixture thereof) (MDI), 4,4'-toluidine isocyanate (TODI), 4,4'-diphenyl ether diisocyanate, xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or a mixture thereof) (XDI), tetramethyl xylylene diisocyanate (1,3- or aromatic polyisocyanates selected from 1,4-tetramethylxylylene diisocyanate or mixtures thereof (TMXDI), ω,ω'-diisocyanato-1,4-diethylbenzene, naphthalene diisocyanate (1,5-, 1,4-, or 1,8-naphthalene diisocyanate or mixtures thereof) (NDI), triphenylmethane triisocyanate, tris(isocyanatophenyl)thiophosphate, polymethylene polyphenylene polyisocyanate, nitrodiphenyl-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, and 3,3'-dimethoxydiphenyl-4,4'-diisocyanate; acyclic aliphatic polyisocyanates selected from trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), hexamethylene diisocyanate, pentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylcaprate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, trimethylhexamethylene diisocyanate, and decamethylene diisocyanate; 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), methylenebis(cyclohexyl isocyanate) (4,4'-, 2,4'- or 2,2'-methylenebis(cyclohexyl isocyanate or a mixture thereof) (hydrogenated MDI), methylcyclohex Cycloalicyclic polyisocyanates selected from diisocyanates (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, bis(isocyanatomethyl)cyclohexane (1,3- or 1,4-bis(isocyanatomethyl)cyclohexane or a mixture thereof) (hydrogenated XDI), dimer acid diisocyanate, transcyclohexane 1,4-diisocyanate, hydrogenated tolylene diisocyanate (hydrogenated TDI), and hydrogenated tetramethylxylylene diisocyanate (hydrated TMXDI); a bridged cycloaliphatic polyisocyanate selected from norbornene diisocyanate, norbornane diisocyanate methyl, bicycloheptane triisocyanate, diisocyanatomethyl bicycloheptane, and di(diisocyanatomethyl)tricyclodecane; TIFF2025114516000022.tif15584 Compounds selected from TIFF2025114516000023.tif209118; and biuret-modified products of the above-mentioned isocyanates, polymers of polyisocyanates (for example, dimers, trimers (for example, isocyanurate derivatives, iminooxadiazinedione derivatives), pentamers, heptamers, etc.), allophanate derivatives (for example, allophanate derivatives produced by the reaction of the above-mentioned polyisocyanates with monohydric alcohols or dihydric alcohols), polyol derivatives (for example, polyol derivatives (alcohol adducts, preferably trimethylolpropane) produced by the reaction of the above-mentioned polyisocyanates with trihydric alcohols (for example, trimethylolpropane, etc.)), Examples of suitable amine derivatives include amine adducts, biuret derivatives (for example, biuret derivatives formed by the reaction of the above-mentioned polyisocyanates with water or amines), urea derivatives (for example, urea derivatives formed by the reaction of the above-mentioned polyisocyanates with diamines), oxadiazinetrione derivatives (for example, oxadiazinetrione formed by the reaction of the above-mentioned polyisocyanates with carbon dioxide), carbodiimide derivatives (for example, carbodiimide derivatives formed by the decarboxylation condensation reaction of the above-mentioned polyisocyanates), uretdione derivatives, and uretonimine derivatives.

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

[0463] [Method for synthesizing isocyanate derivatives]

[0464] To obtain an isocyanate derivative, an active hydrogen compound is reacted with a starting isocyanate. The reaction may be carried out in one step or in multiple successive steps. For example, if the product contains unreacted active hydrogen groups or active hydrogen-reactive groups, the synthesis may be carried out successively. Successive reactions are particularly useful when using a substituted sugar alcohol with a high OH number. 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 starting isocyanate may be blended so that the equivalent ratio of active hydrogen-reactive groups (isocyanate groups) to active hydrogen groups (active hydrogen-reactive groups / active hydrogen groups) is, for example, 1.2 or more, preferably 1.5 or more, and, for example, 2.0 or less.

[0465] [Composition of isocyanate derivative] 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, and may 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, based on the isocyanate derivative.

[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, and may 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, based on the portion derived from the active hydrogen compound.

[0467] The amount of the portion derived from the sugar alcohol / hydroxy acid modified product (α2) 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 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.

[0468] The amount of the portion derived from the cationic active hydrogen compound (α3) 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, and may 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, based on the portion derived from the active hydrogen compound.

[0469] The amount of the portion derived from the other active hydrogen-containing compound (α4) 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, and may 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, relative to the portion derived from the active hydrogen compound.

[0470] The amount of the portion derived from the raw 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, and may 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, based on the isocyanate derivative.

[0471] 〔silicone〕 Silicone will be described as an example of a liquid-repellent compound. The repellent agent in the present disclosure may contain silicone (polyorganosiloxane). By containing silicone, it is possible to achieve good texture and durability in addition to the good liquid-repellency derived from the polysiloxane structure.

[0472] The silicone is a compound mainly composed of a polyorganosiloxane structure, and may be an unmodified silicone (polyalkylsiloxane, polyalkylphenylsiloxane, polydimethylsiloxane, etc.) in which the reactive group is not modified, or may be a modified silicone (amino-modified, epoxy-modified silicone, carboxy-modified silicone, methylhydrogen silicone, etc.).

[0473] The polyorganosiloxane structure of silicone is the same as that described above in (polysiloxane group), and the same description is incorporated herein.

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

[0475] The number of silicon atoms in 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, and is preferably 10 or more, and may be 50,000 or less, 25,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 3,000 or less, 1,500 or less, 1,000 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less, for example, 500 or less.

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

[0477] [Dispersant] The repellent of the present disclosure may contain a dispersant. The dispersant may be at least one selected from an organic dispersant and an inorganic dispersant. The dispersant may be at least one selected from an anionic dispersant, a nonionic dispersant, a cationic dispersant, an amphoteric dispersant, and an inorganic dispersant. In particular, the repellent of the present disclosure may contain a nonionic dispersant.

[0478] As the dispersant, an organic dispersant and an inorganic dispersant may be used individually, or a combination of an organic dispersant and an inorganic dispersant may be used.

[0479] An organic dispersant may be used as the dispersant. The organic dispersant can be classified into a nonionic dispersant, an anionic dispersant, a cationic dispersant, and an amphoteric dispersant, and the organic dispersant may refer to a surfactant.

[0480] The dispersant may not have a fluorine atom.

[0481] [Nonionic dispersant] The dispersant may include a nonionic dispersant, which may be a nonionic surfactant.

[0482] The nonionic dispersant may be a low molecular weight type (e.g., a molecular weight of 2000 or less, particularly 10,000 or less) or a high molecular weight type (e.g., a molecular weight of 2000 or more). The molecular weight of the nonionic dispersant may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 25,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 2500 or less, 750 or less, or 250 or less.

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

[0484] An example of an ether is a compound having an oxyalkylene group (preferably a polyoxyethylene group).

[0485] An example of the ester is an ester of an alcohol and a fatty acid. An example of the alcohol is a mono- to trideca-hydric (particularly di- to deca-hydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 10 to 30 carbon atoms). An example of the fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0486] An example of an ester ether is a compound in which an alkylene oxide (particularly ethylene oxide) is added to an ester of an alcohol and a fatty acid. An example of an alcohol is a mono- to trideca-hydric (particularly di- to deca-hydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms). An example of a fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0487] An example of an alkanolamide is formed from a fatty acid and an alkanolamine. The alkanolamide may be a monoalkanolamide or a dialkanolamine. An example of a fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. The alkanolamine may be an alkanol having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, and having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

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

[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 in the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic dispersant is generally preferably 2 to 100.

[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 a linear and / or branched aliphatic (saturated and / or unsaturated) group, a polyalkylene glycol ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a sorbitan ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a glycerin ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyglycerin ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a sucrose ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of acetylene glycol, or the like. Among these, those in which the structure of the alkylene oxide adduct moiety and the polyalkylene glycol moiety is polyoxyethylene (POE) or polyoxypropylene (POP) or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred. Additionally, the nonionic dispersant may be free of aromatic groups.

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

[0493] R 1R preferably has 8 to 20 carbon atoms, particularly 10 to 18 carbon atoms. 1 Preferred specific examples include an octyl group, a nonyl group, a trimethylnonyl group, a lauryl group, a tridecyl group, an oleyl group, and a stearyl group. R 2 Examples of the alkyl group include a propylene group and a butylene group. In the nonionic dispersant, p may be a number of 3 or more (for example, 5 to 200). q may be a number of 2 or more (for example, 5 to 200). That is, -(R 2 O) q - may form a polyoxyalkylene chain. The nonionic dispersant may be a polyoxyethylene alkylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) at the center. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, and a styrene chain, with the oxypropylene chain being preferred.

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

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

[0496] [Cationic dispersant] The dispersant may include a cationic dispersant. The cationic dispersant may be a cationic surfactant. The cationic dispersant may be a compound having no amide group.

[0497] The cationic dispersant may be a low molecular weight type (e.g., a molecular weight of 2000 or less, particularly 10,000 or less) or a high molecular weight type (e.g., a molecular weight of 2000 or more). The molecular weight of the cationic dispersant may be 100 or more, 500 or more, 1,000 or more, 2,000 or more, 4,000 or more, or 6,000 or more, or may be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 25,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 2,500 or less, 750 or less, or 250 or less.

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

[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. R 21 , R 22 , R 23 and -R 24 Specific examples of X include alkyl groups (e.g., methyl, butyl, stearyl, and palmityl groups) and aromatic groups (e.g., benzyl and phenyl groups). Specific examples of X include halogens (e.g., chlorine) and acids (e.g., hydrochloric acid and acetic acid). Examples of cationic dispersants include monoalkyltrimethylammonium salts (alkyl having 4 to 40 carbon atoms) and benzalkonium chloride.

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

[0501] Low molecular weight cationic dispersants include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydropolyoxyethylene)ammonium chloride, benzyldodecyldi(hydropolyoxyethylene)ammonium chloride, N-[2-(diethylamino)ethyl]oleamide hydrochloride, and the like.

[0502] The polymeric cationic dispersant may be any of various polymers (e.g., polyquaternium-1 to 47) having cationic groups (e.g., ammonium groups, quaternary ammonium groups). Examples of polymeric cationic dispersants include cationic natural products (particularly cationic sugars) such as cationic starch, cationic cellulose (e.g., O-(2-hydroxy-3-(trimethylammonio)propylhydroxyethylcellulose chloride), cationic guar gum, cationic xanthan gum, and chitosan; and polymers of cationic group-containing monomers such as aziridine, vinylimidazole, aminoalkyl methacrylate, N,N,N',N'-tetramethyl-2-butene-1,4-diamine, quaternized dimethylammonium ethyl methacrylate, diallyldimethylammonium chloride, dimethylaminopropylamine, and quaternized vinylimidazole.

[0503] [Anionic dispersant] The dispersant may include an anionic dispersant. The anionic dispersant may be an anionic surfactant. The dispersant may be free of an anionic dispersant.

[0504] The anionic dispersant may be a low molecular weight type (e.g., a molecular weight of 2000 or less, particularly 10,000 or less) or a high molecular weight type (e.g., a molecular weight of 2000 or more). The molecular weight of the anionic dispersant may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 25,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 2500 or less, 750 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-sulfonic acid salts, N-acylamino acid dispersants, phosphate mono- or diester dispersants, and sulfosuccinates. An example of an anionic dispersant is a carboxylate (e.g., a fatty acid salt).

[0506] [Amphoteric dispersant] The dispersant may comprise an amphoteric dispersant, which may be an amphoteric surfactant.

[0507] The amphoteric dispersant may be a low molecular weight type (e.g., molecular weight of 2000 or less, particularly 10,000 or less) or a high molecular weight type (e.g., molecular weight of 2000 or more). The molecular weight of the amphoteric dispersant may be 100 or more, 500 or more, 1,000 or more, 2,000 or more, 4,000 or more, or 6,000 or more; or may be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 25,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 2,500 or less, 750 or less, or 250 or less.

[0508] Examples of amphoteric dispersants include alanines, imidazolinium betaines, amido betaines, and acetic acid betaine, and specific examples include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylamino acetic acid betaine, and fatty acid amidopropyl dimethylamino acetic acid betaine.

[0509] [Inorganic dispersant] The dispersant may include an inorganic dispersant.

[0510] The average primary particle size of the inorganic dispersant may be 5 nm or more, 30 nm or more, 100 nm or more, 1 μm or more, 10 μm or more, or 25 μm or more, and may be 100 μm or less, 50 μm or less, 10 μm or less, 1 μm or less, 500 nm or less, or 300 nm or less. The average primary particle size can be measured, for example, by observation with a microscope (scanning electron microscope or transmission electron microscope). The inorganic dispersant may be hydrophilic particles.

[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, relative to 100 parts by weight of the liquid repellent compound, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less.

[0513] [Liquid medium] The repellent agent of the present disclosure may include a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The repellent agent may be a dispersion or a solution. The repellent agent of the present disclosure is preferably a water dispersion.

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

[0515] [Amount of liquid medium] The amount of the liquid medium may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 1 part by weight of the liquid repellent compound.

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

[0517] The amount of the organic solvent may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, or may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 1 part by weight of the liquid repellent compound.

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

[0519] [Amount of organic acid] The amount of organic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, 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, relative to 100 parts by weight of the liquid repellent compound. 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 of the present disclosure may contain an inorganic acid. Known inorganic acids can be used. Examples of inorganic acids include hydrogen chloride, hydrogen bromide, hydrogen iodide, nitric acid, boric acid, sulfuric acid, and phosphoric acid. In the present disclosure, one type of inorganic acid may be used, or two or more types may be used in combination. Addition of 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, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the liquid repellent compound. 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] [Curing agent] The repellent of the present disclosure may contain a hardening agent (an active hydrogen-reactive compound or an active hydrogen-containing compound). When the repellent is for paper (e.g., an oil-proofing agent for paper), it does not need to contain a hardening agent.

[0523] The curing agent (crosslinking agent) in the repellent agent can cure the agent well. The curing agent may be an active hydrogen-reactive compound or an active hydrogen-containing compound that reacts with active hydrogen or an active hydrogen-reactive group. Examples of active hydrogen-reactive compounds 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 functions as a crosslinking agent. Examples of polyisocyanate compounds include aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates. The isocyanate compound may be a blocked isocyanate compound (for example, a blocked polyisocyanate compound). A blocked isocyanate compound is a compound in which the isocyanate group of an isocyanate compound is masked with a blocking agent to inhibit reaction.

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

[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 alone or in combination of two or more.

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

[0528] Examples of aromatic polyisocyanates include aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate or a mixture thereof, 2,4- or 2,6-tolylene diisocyanate or a mixture thereof, triphenylmethane-4,4',4''-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate. These may be used alone or in combination of two or more.

[0529] Examples of the polyisocyanate derivatives include various derivatives of the above-mentioned polyisocyanate compounds, such as dimers, trimers, biurets, allophanates, carbodiimides, uretdiones, uretimines, isocyanurates, and iminooxadiazinediones. These may be used alone or in combination of two or more.

[0530] These polyisocyanates can be used alone or in combination of two or more. As the polyisocyanate compound, it is preferable to use a blocked polyisocyanate compound (blocked isocyanate), which is a compound in which the isocyanate group of a polyisocyanate compound is blocked with a blocking agent.The use of a blocked polyisocyanate compound is preferable for reasons such as its relative stability in solution and its usability in the same solution as the repellent.

[0531] The blocking agent blocks free isocyanate groups. When the blocked polyisocyanate compound is heated to, for example, 100°C or higher, e.g., 130°C or higher, the isocyanate groups are regenerated and can easily react with hydroxyl groups. Examples of blocking agents include phenolic compounds, lactam compounds, aliphatic alcohol compounds, and oxime compounds. The polyisocyanate compounds can be used alone or in combination.

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

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

[0534] [Amount of hardener] The amount of the curing agent may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the liquid repellent compound, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0535] [Other ingredients] The repellent may contain other components in addition to the above components. Examples of the other components include polysaccharides, flocculants, retention aids, coagulants, binder resins, anti-slip agents, sizing agents, paper strength agents, fillers, antistatic agents, preservatives, ultraviolet absorbers, antibacterial agents, deodorizers, fragrances, etc. These may be used alone or in combination of two or more. In addition to the above-mentioned components, other ingredients may include repellents (water and / or oil repellents, etc.), dispersants, texture modifiers, softeners, flame retardants, paint fixatives, wrinkle inhibitors, drying speed regulators, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, insect repellents, defoamers, shrinkage inhibitors, anti-wrinkle agents, shape retention agents, drape retention agents, ironing improvers, whitening agents, whitening agents, fabric softening clay, dye transfer inhibitors such as polyvinylpyrrolidone, polymer dispersants, stain release agents, scum dispersants, fluorescent whitening agents such as 4,4-bis(2-sulfostyryl)biphenyl disodium (Ciba Specialty Chemicals' Tinopal CBS-X), dye fixatives, and colorfastness inhibitors such as 1,4-bis(3-aminopropyl)piperazine. These agents include detergents, stain removers, enzymes such as cellulase, amylase, protease, lipase, and keratinase as fiber surface modifiers, foam inhibitors, and agents that can impart silk texture and functionality such as moisture absorption and release, such as silk protein powder, surface-modified products, or emulsified dispersions thereof (e.g., K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemicals), hydrolyzed silk liquid (Jomo), Silkgen G Soluble S (Ichimaru Falcos)), and stain-preventing agents (e.g., nonionic polymer compounds composed of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units (e.g., FR627 manufactured by GOO Chemical Industry Co., Ltd., SRC-1 manufactured by Clariant Japan). These agents may be used alone or in combination. The ingredients may be appropriately selected depending on the intended use of the repellent.

[0536] [Amount of other ingredients] The amount of each or the total amount of the other components may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the liquid repellent compound, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0537] <Pulp composition> The pulp composition according to the present disclosure includes a liquid repellent compound and a pulp base material. The pulp composition according to the present disclosure may have excellent oil resistance.

[0538] The pulp composition of the present disclosure can be obtained by adding a liquid-repellent compound to a pulp base material. The pulp composition can be obtained by treating the pulp base material with a repellent containing the liquid-repellent compound, and the amount of repellent added and the composition of the repellent can be adjusted so that each component is present in a desired amount. Each component that can be contained in the repellent can be added to the pulp composition as a separate additive.

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

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

[0541] [Pulp base 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, or the like.

[0542] [Wood pulp] Wood pulp includes softwood kraft pulp obtained from species such as fir and pine, and hardwood kraft pulp obtained from species such as acacia, eucalyptus, beech, and poplar (e.g., poplar). Examples of softwood kraft pulp include unbleached softwood kraft pulp (NUKP), bleached softwood pulp (NBKP), semi-bleached softwood kraft pulp (NSBKP), and softwood sulfite pulp. Examples of hardwood kraft pulp include unbleached hardwood kraft pulp (LUKP), bleached hardwood kraft pulp (LBKP), semi-bleached hardwood kraft pulp (LSBKP), and hardwood sulfite pulp. The pulps used may be used alone or in combination. In addition to kraft pulp, there are softwood kraft pulp and hardwood kraft pulp, as well as mechanical pulps such as stone ground pulp (SGP), pressurized stone ground pulp (PGW), refiner ground pulp (RGP), thermoground pulp (TGP), chemiground pulp (CGP), groundwood pulp (GP), and thermomechanical pulp (TMP).Furthermore, waste paper pulp includes disintegrated waste paper pulp, disintegrated and deinked waste paper pulp, and disintegrated, deinked, and bleached waste paper pulp, which are produced from brown paper, recycled kraft envelope paper, magazine paper, newspaper paper, flyer paper, office paper, corrugated cardboard, white paper, Kent paper, imitation paper, and land certificate paper.

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

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

[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 is preferably 50 μm or less, more preferably 40 μm or less, even more preferably 30 μm or less.

[0546] [Pulp base material form] The form of the pulp base material when the liquid-repellent compound is added may be pulp alone, pulp slurry, pulp products, etc., and specific examples include pulp such as bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulp such as groundwood pulp, mechanical pulp or thermomechanical pulp; pulp slurries containing the above pulp; and pulp products such as paper, paper containers, and pulp molded products.

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

[0548] The amount of the pulp base material may be 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, 90% by weight or more, 95% by weight or more, or 99% by weight or more in the pulp composition excluding the liquid medium, and may be 99.9% by weight or less, 95% by weight or less, 90% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, or 55% by weight or less.

[0549] [Liquid medium] The pulp composition may include a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent, typically an aqueous medium (water or a mixture of water and an organic solvent), especially water. The liquid medium may include a liquid medium derived from a repellent agent.

[0550] [Amount of liquid medium] The amount of the liquid medium in the pulp composition may be 0.1% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 50% by weight or more, 75% by weight or more, 90% by weight or more, or 95% by weight or more, and may be 99% by weight or less, 75% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, 4% by weight or less, or 3% by weight or less. Typically, when the pulp composition is prepared by internal addition, the amount of the liquid medium in the pulp composition is 50% by weight or more, particularly 90% by weight or more, and when the pulp composition is prepared by external addition, the amount of the liquid medium in the pulp composition may be 30% by weight or less, particularly 10% by weight or less.

[0551] [Liquid repellent compound] The pulp composition contains a liquid-repellent compound. For details of the liquid-repellent compound, the explanation of the liquid-repellent compound in the above <Repellent Agent> is incorporated herein by reference.

[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, and is preferably 0.03% by weight or more, for example 0.5% by weight or more, and may be 25% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, for example 15% by weight or less or 5.0% by weight or less, and preferably 3.0% by weight or less.

[0553] The liquid-repellent compound may be added externally to the surface of a pulp substrate (for example, a pulp product such as paper, a paper container, or a pulp molded product), and the amount of the liquid-repellent compound contained in the coating layer formed by the external addition treatment is 0.01 g / m 2 More than 0.03g / m 2 More than 0.05g / m 2 More than 0.1g / m 2 More than 0.3g / m 2 More than 0.5g / m 2 or more, or 1.0 g / m 2 or more, and 5.0 g / m 2 Below 4.0g / m 2 Below 3.0g / m 2 Below 2.0g / m 2 Below 1.0g / m 2 Below 0.5g / m 2 Below 0.3g / m 2 or less, or 0.1 g / m 2 It may be the following:

[0554] [Lignin Compounds] The pulp composition preferably contains a lignin compound. For details of the lignin compound, the explanation of the lignin compound in <Repellent Agent> is incorporated herein by reference.

[0555] [Amount of lignin compounds] The amount of lignin compounds may be 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more, and may be 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, preferably 5.0% by weight or less, more preferably 3.0% by weight or less, based on the pulp base material.

[0556] [Dispersant] The pulp composition may contain a dispersant. For details of the dispersant, the description of the dispersant in <Repellent Agent> is incorporated herein by reference.

[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, and may be 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, preferably 5.0% by weight or less, more preferably 3.0% by weight or less, based on the pulp base material.

[0558] [Paper strength agent] The pulp composition may include a strength agent. Examples of strength agents include: Polyacrylamide-based paper strength agents such as cationic polyacrylamide, anionic polyacrylamide, and amphoteric polyacrylamide; polysaccharide-based paper strength agents such as starch, enzyme-modified starch, thermochemically modified starch, oxidized starch, esterified starch, etherified starch (e.g., hydroxyethylated starch), aldehyde starch, cationized starch, starch, xanthan gum, karaya gum, welan gum, guar gum, pectin, tamarind gum, carrageenan, chitosan, gum arabic, locust bean gum, cellulose, alginic acid, agar, dextran, cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, chitin nanofiber, cellulose nanofiber, and pullulan, and modified polysaccharides thereof (e.g., modified polysaccharides into which hydroxyl groups or cationic groups have been introduced); Polyamide-based paper strength agents such as polyamide resins, polyamine resins, polyamide-polyamine resins, polyamide-epichlorohydrin resins, polyamide-polyamine-epichlorohydrin resins, polyamide-polyurea-formaldehyde resins, and epoxidized polyamide resins; Urea / melamine-based paper strength agents such as urea resin, melamine resin, urea-formaldehyde resin, and melamine-formaldehyde resin; polyvinyl alcohol-based paper strength agents such as polyvinyl alcohol, fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, cation-modified polyvinyl alcohol, and terminal alkyl-modified polyvinyl alcohol; Examples include styrene-butadiene copolymer, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, polyacrylic ester, fatty acid diamide, polyethyleneimine resin, and ketone aldehyde resin. The paper strength agent in the present disclosure is preferably a polyacrylamide-based paper strength agent, a polysaccharide-based paper strength agent, or a polyamide-based paper strength agent.

[0559] [Amount of paper strength agent] The amount of the paper strength agent may be 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more, and may be 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, and is preferably 5.0% by weight or less, based on the pulp.

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

[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, and may be 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, based on the pulp.

[0562] [Other additives] In addition to the above, the pulp composition may contain other additives such as known paper additives used in the production of pulp products, such as fixing agents (water-soluble aluminum compounds such as aluminum sulfate and polyaluminum chloride), coagulants / flocculants (polyamine resins, etc.), retention aids (polyacrylamide resins, etc.), organic acids (formic acid, acetic acid, etc.), dyes, slime control agents, and antifoaming agents.

[0563] [Amount of other additives] The amount of the other additives may be 0.01% by weight or more, 0.1% by weight or more, 1% by weight or more, 3% by weight or more, or 5% by weight or more, and may be 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, 3% by weight or less, or 1% by weight or less, based on the pulp base material.

[0564] <Product manufacturing method> A method for producing a product according to the present disclosure may include a step of treating a substrate with the repellent according to the present disclosure as a treatment agent.

[0565] The substrate to be treated with the treatment agent of the present disclosure is not limited, but is preferably a fibrous substrate, particularly a textile substrate or a pulp substrate, and is particularly a pulp substrate.

[0566] Examples of fiber substrates include natural fibers of animal or plant origin such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semi-synthetic fibers such as rayon and acetate, inorganic fibers such as glass fiber, carbon fiber, and asbestos fiber, or mixtures of these fibers. Fiber products include woven fabrics, knitted fabrics, and nonwoven fabrics, as well as cloth in the form of clothing (for example, water-repellent clothing such as raincoats) and carpets, but the treatment may also be applied to fibers, yarns, and intermediate fiber products (for example, slivers or rovings) in a state prior to being made into cloth.

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

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

[0569] [Method for manufacturing pulp products] The pulp product (paper product) in the present disclosure can be obtained by treating a pulp base material with a repellent containing a liquid-repellent compound to obtain a pulp composition, and then subjecting the pulp composition to treatment steps such as drying, heating, molding, etc. as necessary. The pulp product may be an oil-resistant pulp product that has been treated with an oil-proofing agent.

[0570] The repellent agent of the present disclosure can be applied to a pulp substrate as a treatment agent (particularly a surface treatment agent) by a conventionally known method. The treatment method may involve dispersing and diluting the repellent agent of the present disclosure in an organic solvent or water, as necessary, and applying it to the interior and / or surface of the pulp substrate by a known method such as dip coating, spray coating, or foam coating, followed by drying. The dilution ratio may be varied as appropriate 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 is obtained to which the solid components of the repellent agent are attached. If necessary, the repellent agent may be applied together with an appropriate crosslinking agent, followed by curing.

[0571] The repellent agent can be applied to the pulp substrate by any of the known methods for treating a pulp substrate with a liquid. The pulp substrate may be immersed in the repellent agent, the pulp substrate and the repellent agent may be mixed, or the solution may be applied 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 the present disclosure, the heating time may be 5 seconds to 60 minutes, for example, 30 seconds to 3 minutes.

[0572] Pulp substrate treatment methods can include internal treatment methods in which a repellent is added to the pulp substrate (e.g., in the form of pulp slurry) before papermaking, or external treatment methods in which a repellent is applied to the pulp substrate (e.g., pulp product) after papermaking. Examples of internal treatment methods include mixing and immersion, which may include a step of adding a repellent to the pulp slurry and stirring and mixing it. Examples of external treatment methods include spraying, coating, immersion, and foam application, and specific examples include pond-type two-roll size presses, gate-roll type, and rod-metering size presses. The treatment may be either an external or internal treatment. For example, when the pulp substrate is paper, the repellent may be coated on the paper, or a solution may be attached or sprayed onto the paper, or the repellent may be mixed with the pulp slurry before papermaking. When the pulp substrate is a fibrous material, treatment methods include padding, immersion, spraying, and coating. Examples of padding treatments include methods using padding devices described on pages 396-397 of "Textile Dyeing and Processing Dictionary" (published by Nikkan Kogyo Shimbun, 1963) and pages 256-260 of "Color Dyeing Chemistry III" (published by Jikkyo Publishing Co., Ltd., 1975). Examples of coating treatments include methods using coating machines described on pages 473-477 of "Dyeing and Finishing Equipment Directory" (published by Sen-sha, 1981). Examples of immersion treatments include methods using batch dyeing machines described on pages 196-247 of "Dyeing and Finishing Equipment Directory" (published by Sen-sha, 1981). Examples of suitable dyeing machines include liquid jet dyeing machines, air jet dyeing machines, drum dyeing machines, winch dyeing machines, washer dyeing machines, and cheese dyeing machines. Examples of spray treatments include methods using air sprayers that spray the treatment solution in a mist using compressed air, and hydraulic atomization air sprayers.

[0573] The treatment method may be an internal addition treatment in which a repellent is added to a pulp slurry before papermaking. The internal addition treatment may include filling the pulp slurry into a mold and allowing a liquid medium to permeate out of the mold to form pulp. For example, the internal addition treatment may include one or more of the following steps: adding a repellent to the pulp slurry and stirring and mixing it; suction-dehydrating the pulp composition prepared in the above step through a mesh of a predetermined shape to deposit the pulp composition and form a molded pulp product intermediate; and molding and drying the molded pulp product intermediate in a heated mold to obtain a molded pulp product. The treated paper may be simply dried at room temperature or at an elevated temperature, and then optionally subjected to a heat treatment depending on the paper's properties. The heat treatment temperature may be 150°C or higher, 180°C or higher, or 210°C or higher, or 300°C or lower, 250°C or lower, or 200°C or lower, and particularly preferably 80°C to 180°C. Heat treatment within this temperature range can exhibit excellent oil resistance, etc. The internally treated pulp base material may be treated with a repellent by external addition, and further liquid repellent compounds or repellents may be attached to the surface.

[0574] The treatment method may be an external addition treatment in which a repellent agent is applied to the pulp base material after papermaking. Size presses for external addition treatment can also be classified as follows based on the application method. One application method is the so-called pond-type two-roll size press, in which a coating liquid (size liquid) is supplied to the nip formed by passing paper between two rubber rolls, creating a coating liquid pool called a pond, and the paper is passed through this coating liquid pool to apply the sizing liquid to both sides of the paper. Other application methods include the gate roll type, in which the sizing liquid is applied using a surface transfer method, and the rod metering size press. In the pond-type two-roll size press, the sizing liquid easily penetrates into the paper, while in the surface transfer type, the sizing liquid components tend to remain on the paper surface. In the surface transfer type, the coating layer tends to remain on the paper surface compared to the pond-type two-roll size press, and the coating layer formed on the surface is larger than in the pond-type two-roll size press. In the present disclosure, performance can be imparted to paper even when the former pond-type two-roll size press is used. Papers treated in this way can exhibit excellent oil resistance etc., optionally after simple drying at room temperature or elevated temperature followed by a heat treatment which, depending on the properties of the paper, can range from 300°C, for example up to 200°C, in particular from 80°C to 180°C.

[0575] Specific examples of pulp products include paper, paper containers, pulp molded products, food packaging materials, food containers, gypsum board base paper, coated base paper, medium paper, general liners and corrugating media, neutral white roll paper, neutral liners, rust-proof liners and metal interleaving paper, kraft paper, neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper, and neutral information paper, etc. Suitable examples of pulp products include food packaging materials and food containers, such as pulp products for food contact applications, particularly pulp molded products for food contact applications.

[0576] Although the embodiments have been described above, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims. [Example]

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

[0579] [High temperature oil resistance] 100 ml of the evaluation liquid (corn oil) at 65°C was poured into a pulp molded product formed into a container and left to stand for 45 minutes, or 100 ml of the evaluation liquid (corn oil) at 80°C was poured into the product and left to stand for 30 minutes, a...

Claims

1. An oil-resistant agent comprising a liquid-repellent compound and a lignin compound.

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

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

4. 3. The oil-proofing agent according to claim 1, wherein the lignin compound is sodium lignosulfonate.

5. 3. The oil-resistant agent according to claim 1, 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 a substituent, and a polysiloxane group.

6. 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-modified compounds, polyol-modified compounds, polycarboxylic acid-modified compounds, isocyanate derivatives, waxes, and silicones.

7. 6. 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. 3. The oil-resistant agent according to claim 1, wherein the liquid-repellent compound is a (meth)acrylic polymer having a chain alkyl group having from 12 to 18 carbon atoms.

9. 3. The oil-resistant agent according to claim 1, wherein the liquid-repellent compound has a contact angle with hexadecane of 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 a 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 are 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—, Y ａ１２ are each independently a direct bond, or —O—, —C(═O)—, —S(═O) ２ -, -NH- or -CH ２ - is a group consisting of at least one selected from 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 the formula:

12. 3. An oil-resistant pulp product, comprising the liquid-repellent compound and the lignin compound in the oil-resistant agent according to claim 1 or 2, adhered to a pulp substrate.

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

14. 13. The oil-resistant pulp product of claim 12, which is a molded pulp product.

15. 13. The grease-resistant pulp product of claim 12 which is a food packaging or food container.

16. A method for producing an oil-resistant pulp product, comprising a step of treating a pulp base material with the oil-proofing agent according to claim 1 or 2 by external or internal addition.

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