Repellent

Abstract

To provide a new repellent capable of imparting oil resistance to a base material (e.g., fiber and paper).SOLUTION: The present invention provides a water-dispersion type repellent containing a cationic dispersant and a liquid-repelling compound which is at least one selected from the group consisting of polyol modification products and amine modification products.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to repellents and products treated with repellents. [Background technology]

[0002] In recent years, development of non-fluorine-based repellents capable of imparting liquid repellency (water repellency, oil repellency, oil resistance, and / or water resistance) to various substrates has progressed. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2021-155492 A Summary of the Invention [Problem to be solved by the invention]

[0004] Patent Document 1 does not describe oil resistance. Patent Document 1 does not describe the use of a cationic dispersant. Furthermore, Patent Document 1 does not consider the effect of the size of particles contained in the repellent on oil resistance.

[0005] An object of the present disclosure is to provide a novel repellent that can impart oil resistance to a substrate (for example, fiber, paper). [Means for solving the problem]

[0006] The present disclosure includes the following aspects: [Section 1] A liquid repellent compound which is at least one selected from the group consisting of polyol-modified compounds and amine-modified compounds, and Cationic Dispersants A water-dispersible repellent comprising: [Section 2] Item 2. The repellent according to item 1, wherein the volumetric ratio of particles having a size of 1 μm or more is 30% or less as measured by a laser diffraction scattering method. [Section 3] Item 3. The repellent according to item 1 or 2, having an ionic charge density of 1 μeq / g or more and 1000 μeq / g or less. [Section 4] Item 4. The repellent according to any one of items 1 to 3, comprising a nonionic dispersant. [Section 5] the polyol modified product is a compound obtained by modifying a polyol with a monovalent hydrocarbon group having from 1 to 40 carbon atoms, which may have a substituent, or a monovalent polysiloxane group; Item 5. The repellent according to any one of items 1 to 4, wherein the amine-modified product is a compound obtained by modifying an amine with a monovalent hydrocarbon group having 1 to 40 carbon atoms, which may have a substituent, or a monovalent polysiloxane group. [Section 6] the polyol modification is a compound obtained by modifying a polyol with an alkyl group having 6 to 40 carbon atoms; Item 6. The repellent according to any one of items 1 to 5, wherein the amine-modified product is a compound obtained by modifying an amine with an alkyl group having 6 to 40 carbon atoms. [Section 7] The polyol modification comprises modifying one or more hydroxy groups of the polyol to the formula: -YZ n [In the formula, Y is Y 1 and Y 2 is a 1+n valent group consisting of one or more selected from the group consisting of Y 1 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-, -NR'-, -C(OR')R'-, -C(OR')(-)2, -N(-)2 (wherein R' is independently at each occurrence a hydrogen atom or an organic group having 1 to 30 carbon atoms); Y 2 is a group consisting of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent aromatic hydrocarbon rings, and optionally substituted di- to tetravalent heterocycles, Z is a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group which may have a substituent, n is an integer between 1 and 3. A compound substituted with a group represented by the formula: The amine-modified an amine backbone, and The formula: -XZ n [X is X 1 and X 2 is a 1+n valent group consisting of one or more selected from the group consisting of X 1 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-, -NR'-, -C(OR')R'-, -C(OR')(-)2, -N(-)2 (wherein R' is independently at each occurrence a hydrogen atom or an organic group having 1 to 30 carbon atoms); X 2 is a group consisting of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent aromatic hydrocarbon rings, and optionally substituted di- to tetravalent heterocycles, Z is a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group which may have a substituent, n is an integer between 1 and 3. has one or more groups represented by At least one -XZ n is bonded to a nitrogen atom of the amine skeleton. [Section 8] Y of the modified polyol is -OY 11 -or -OY 11 -Y 21 -Y 12 - wherein each symbol represents independently at each occurrence: Y 11is a direct bond, -C(=O)-, -C(=O)-NR'-, or -C(=S)-NR'-; Y 21 is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, Y 12 is -O-, -OC(=O)-, -OC(=O)-O-, -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO2-, -SO2NR'-, -C(OR')R'-, or -C(OR')(-)2. and; The amine-modified The formula: N(-XZ n ) p (-H) q -L 1 -[N(-XZ n ) r (-H) s -L 1 -] t -N(-XZ n ) p (-H) q [In the formula, X and Z are independently in each occurrence as defined above; L 1 represents, 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, independently in each occurrence, is an integer between 1 and 3, inclusive; p, in each occurrence, is an integer greater than or equal to 0 and less than or equal to 2; q, independently in each occurrence, is an integer greater than or equal to 0 and less than or equal to 2; p+q is the sum of each N(-XZ 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(-XZ n ) r (-H) s In, 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. or The formula: N(-XZ n ) p (-H) q -L 2 (-XZ n ) u [In the formula, X and Z are independently in each occurrence as defined above; L 2 represents an aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms and a valence of 1+u, which may be interrupted by an oxygen atom and / or a sulfur atom, n is independently in each occurrence an integer from 1 to 3, optionally interrupted by oxygen and / or sulfur atoms; 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.] 8. The repellent according to any one of items 1 to 7, which is a compound represented by the following formula: [Section 9] the polyol is at least one selected from the group consisting of monosaccharides, oligosaccharides, polysaccharides, sugar alcohols, hydroxy acids, amino acids, vitamins, flavonols, hydroxy hydrocarbons, and hydroxy group-containing compound polymers; Item 9. The repellent according to any one of items 1 to 8, wherein the amine is an organic amine. [Section 10] The polyol is Glucose, fructose, galactose, xylose; Sucrose, cycloamylose, cyclodextrin, maltose, trehalose, lactose, sucralose; Sorbitol, maltitol, erythritol, isomalt, lactitol, mannitol, xylitol, sorbitan, lactitol; Starch, Cellulose, Curdlan, Pullulan, Alginic Acid, Carrageenan, Guar Gum, Chitin, Chitosan, Locust Bean Gum, Kappa Carrageenan, Iota Carrageenan, Isomaltodextrin, Gellan Gum, Tamarind Seed Gum; Ascorbic acid, kojic acid, quinic acid, chlorogenic acid, gluconic acid; Glucosamine; Inositol; Catechins, quercetin, anthocyanins; Glycerin, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, trimethylolpropane, trimethylolethane; At least one selected from the group consisting of polyglycerin, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymers, hydroxypropyl (meth)acrylate polymers, and hydroxybutyl (meth)acrylate polymers; Item 10. The repellent according to any one of items 1 to 9, wherein the amine is at least one selected from the group consisting of alkylenediamines, alkylenetriamines, alkylenetetramines, and aromatic amines. [Section 11] Item 11. The repellent according to any one of items 1 to 10, wherein the cationic dispersant is a quaternary ammonium salt. [Section 12] Item 12. The repellent according to any one of items 1 to 11, wherein the polyol modified product or the amine modified product has a bio-based content of 20% or more. [Section 13] Item 13. The repellent according to any one of items 1 to 12, wherein the amine-modified compound is a polyamide. [Section 14] the liquid repellent compound is the modified polyol, The polyol modification product is a product in which a hydroxy group possessed by a polyglycerol having a polymerization degree of 5 to 15 is substituted with a hydroxy group possessed by a polyglycerol having a polymerization degree of 5 to 15, the hydroxy group being represented by the following formula: -OC(=O)-Z [In the formula, Z is an alkyl group having 14 to 24 carbon atoms. is a compound substituted with a group represented by Item 14. The repellent according to any one of items 1 to 13, wherein the hydroxy group substitution rate in the modified polyol is 50% or more. [Section 15] Item 15. The repellent according to any one of items 1 to 14, which is for textile products or paper products. [Section 16] Item 16. A product treated with the repellent according to any one of items 1 to 15. [Section 17] Item 17. The product according to item 16, which is a textile product or a paper product. [Section 18] Item 18. The product according to item 16 or 17, which is greaseproof or waterproof paper. [Section 19] Item 19. The product according to any one of items 16 to 18, which is a food packaging material or a food container. [Section 20] Item 16. A method for producing a treated product, comprising a step of treating a substrate with the repellent according to any one of items 1 to 15. [Section 21] Item 21. The method according to item 20, wherein the treatment is an internal addition treatment. Effect of the Invention

[0007] The repellent of the present disclosure can impart good liquid repellency (especially oil resistance) to paper products. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] <Terminology> As used herein, the term "n-valent group" refers to a group having n bonds, i.e., a group that forms n bonds. The term "n-valent organic group" refers to an n-valent group containing carbon. Such an organic group is not particularly limited, but may be a hydrocarbon group or a derivative thereof. The derivative of a hydrocarbon group 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 a group obtained by removing a hydrogen atom from a hydrocarbon. Such a hydrocarbon group includes, but is not limited to, C 1-20 Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. 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 occur multiple times in a chemical structure is defined, the 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] It should be understood that the chemical structures illustrated herein do not encompass chemical structures that would be recognized by those of ordinary skill in the art as being chemically impossible or extremely unstable.

[0012] <Repellent>

[0013] The repellent in the present disclosure imparts liquid repellency (water repellency, oil repellency, oil resistance, and / or water resistance) to a substrate (e.g., a fiber substrate, a paper substrate), and can function as at least one selected from the group consisting of a water repellent, an oil repellent, an oil resistance agent, and a water resistance agent. The repellent in the present disclosure can effectively impart oil resistance (oil repellency) and / or water resistance (water repellency) to the substrate, and can, for example, effectively impart both oil resistance and water resistance.

[0014] The repellent in the present disclosure may be a water-dispersible repellent containing a liquid repellent compound that is at least one type selected from the group consisting of polyol modifications and amine modifications, and a cationic dispersant.

[0015] The repellent agent in 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 in the present disclosure can impart liquid repellency to a substrate even if it does not contain these fluorine compounds.

[0016] [Volume ratio of particles] The volumetric ratio of particles of 1 μm or more in the repellent of the present disclosure measured by the laser diffraction scattering method may be 0.1% or more, 3% or more, 5% or more, 10% or more, or 15% or more, and may be 75% or less, 50% or less, 30% or less, 20% or less, 15% or less, 10% or less, 5% or less, 3% or less, 1.5% or less, or 0%, and is preferably 50% or less, or 30% or less. It is preferable that the volumetric ratio of particles of 1 μm or more is in the above range (particularly the upper limit value or less) from the viewpoint of coverage and dispersion stability. The method for making the volumetric ratio of particles of 1 μm or more measured by the laser diffraction scattering method into the above range is not limited, but for example, the particles in the raw material and / or the dispersion may be finely divided using a grinder, homogenizer, or the like.

[0017] [Volume Median Diameter] The volume median diameter of the repellent of the present disclosure measured by the laser diffraction scattering method may be 10 nm or more, 30 nm or more, 50 nm or more, 100 nm or more, preferably 150 nm or more, or 200 nm or more. The volume median diameter may be 10 μm or less, 5 μm or less, 3 μm or less, 1 μm or less, 900 nm or less, 800 nm or less, 700 nm or less, 600 nm or less, 500 nm or less, 400 nm or less, or 300 nm or less, preferably 1 μm or less. In the present disclosure, the volume median diameter refers to the median diameter (D50) in the volume-based particle size distribution measured by the laser diffraction scattering method.

[0018] 〔charge〕 The ionic charge density in the repellent of the present disclosure may be -1000 μeq / g or more, -500 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 1 μeq / g or more, for example 25 μeq / g or more. The ionic charge density in the repellent of the present disclosure may be 5000μeq / g or less, 2500μeq / g or less, 1000μeq / g or less, 750μeq / g or less, 500μeq / g or less, 350μeq / g or less, 300μeq / g or less, 200μeq / g or less, 100μeq / g or less, or 50μeq / g or less, preferably 1000μeq / g or less, more preferably 500μeq / g or less, for example 300μeq / g or less. In particular, the ionic charge density in the repellent of the present disclosure is preferably 1 to 500μeq / g, and more preferably 10 to 250μeq / g (for example, about 50μeq / g, about 100μeq / g, or about 150μeq / g). The ionic charge density in the repellent of the present disclosure can be measured, for example, by the following method.

[0019] The anion demand of a 0.1g / L sample solution is measured using a particle charge meter (BTG MUTEK PCD-04) with a 1 / 1000 N solution of potassium polyvinyl sulfonate, and the ionic charge density (cationic charge density) is calculated using the following formula (1). Alternatively, the cation demand is measured in the same manner 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 solution concentration (g / L)

[0020] [Modified polyol] The modified polyol of the present disclosure can be attached to a substrate and impart liquid repellency, such as oil resistance and water resistance, to the substrate.

[0021] [Characteristics, etc.] The HD (n-hexadecane) contact angle of the polyol-modified product may be 10° or more, 15° or more, 25° or more, 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, or 65° or more, and is preferably 30° or more. The HD contact angle of the polyol-modified product may be 100° or less, 90° or less, or 75° or less. When the polyol-modified product 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 polyol-modified product with respect to the spin-coated film as shown in the examples, and is obtained by dropping 2 μL of HD on the spin-coated film and measuring the contact angle 1 second after the drop lands.

[0022] The water contact angle of the polyol-modified product 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 polyol-modified product 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 polyol-modified product with respect to the spin-coated film as shown in the examples, 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.

[0023] The polyol modification is preferably a compound having carbon of bio-based origin. The bio-based degree is measured in accordance with ASTM D6866. The bio-based degree 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 bio-based degree means that a small amount of fossil resource-based materials, such as petroleum, is used, and from this perspective, the higher the bio-based degree of the polyol modification, the more preferable it is.

[0024] The biodegradability of the polyol-modified product after 180 days is preferably 5% or more. Since the environmental load is reduced, the higher the biodegradability, the more preferable. The biodegradability of the polyol-modified product 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 60% or more, more preferably 70% or more, even more preferably 80% or more, and most preferably 90% or more. The biodegradability of the polyol-modified product after 60 days is preferably 5% or more. Since the environmental load is reduced, the higher the biodegradability, the more preferable. The biodegradability of the polyol-modified product 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 50% or more, more preferably 60% or more. Such biodegradability may be the biodegradability defined in JIS K 6953-1 or ASTM D6400.

[0025] [Structure, etc.] The modified polyol in the present disclosure may not 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 modified polyol does not contain these fluorine-containing groups, it can impart liquid repellency to a substrate.

[0026] The polyol modified product may be a polymer having a degree of polymerization of 1 or more. From the viewpoint of improving liquid repellency, the degree of polymerization of the polyol modified product may be 2 or more, 3 or more, 5 or more, 6 or more, preferably 7 or more, more preferably 8 or more, and even more preferably 9 or more, and from the viewpoint of improving the handleability of the repellent, it may be 100 or less, preferably 50 or less, more preferably 30 or less, even more preferably 15 or less, and particularly preferably 12 or less. The degree of polymerization means the number of repeating monomer units constituting the polymer.

[0027] The degree of polymerization in the present disclosure means an average degree of polymerization. The average degree of polymerization in the present disclosure means a degree of polymerization measured under the following conditions. In the present disclosure, when the polyol modified product is a polyglycerin modified product obtained by modifying polyglycerin, the degree of polymerization of the polyol modified product means the average degree of polymerization of the polyglycerin. The average degree of polymerization of polyglycerin is the average degree of polymerization (n) calculated from the hydroxyl value by the terminal group analysis method. In detail, 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 is an index of 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 "Standard Methods for Analysis of Fats, Oils and Related Compounds (I), 2003 Edition, Established by the Japan Oil Chemists' Society." The hydroxyl value of the raw material polyglycerol is actually measured according to the above-mentioned Standard Methods for Analysis of Fats, Oils and Related Compounds, and the average degree of polymerization and average molecular weight of polyglycerol can be calculated from the above-mentioned formula.

[0028] In the present disclosure, when the polyol modified product is a polyvinyl alcohol modified product obtained by modifying polyvinyl alcohol, the degree of polymerization of the polyol modified product means the average degree of polymerization of the polyvinyl alcohol. The average degree of polymerization of polyvinyl alcohol can be measured in accordance with JIS K 6726 polyvinyl alcohol test method.

[0029] In the present disclosure, when the polyol-modified product is a polysaccharide-modified product obtained by modifying a polysaccharide, the degree of polymerization of the polyol-modified product means the average degree of polymerization of the polysaccharide. The average degree of polymerization of a polysaccharide can be analyzed as follows. The degree of polymerization is the number of monosaccharide units (fructose and glucose units) in the polysaccharide, and the average degree of polymerization is, for example, the average degree of polymerization determined by the top of the peaks of each analysis result obtained by a normal analysis method such as HPLC, GC, and HPAEC as follows. The measurement can be performed by using, for example, ULTRON PS-80N (8×300 mm) (solvent: water, flow rate: 0.5 ml / min, temperature: 50° C.) manufactured by Shinwa Chemical Industry Co., Ltd. or TSK-GEL G30000 PWXL (7.8×300 mm) (solvent: water, flow rate: 0.5 ml / min, temperature: 50° C.) manufactured by TOSOH Co., Ltd. as a column, and a differential refractometer as a detector.

[0030] 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 modification may be 100 or more, 200 or more, 300 or more, 400 or more, 500 or more, 1000 or more, 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 30000 or more, or 500000 or more; and may be 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, 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.

[0031] The substitution rate of the hydroxyl group in the polyol modification 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" means the proportion (mol%) of the hydroxyl group derived from the polyol that is modified, and may mean the proportion (mol%) of the hydroxyl group that is modified with a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group that may have a substituent.

[0032] The residual rate of hydroxyl groups in the polyol modification 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 rate" refers to the proportion (mol%) of hydroxyl groups derived from the polyol that are not modified.

[0033] 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 or a monovalent polysiloxane group which may have a substituent.

[0034] 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. It is the value obtained by dividing the weight average molecular weight of the polyol modified product by the number of modifying groups. Here, the modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have a substituent.

[0035] In the polyol modification, one or more hydroxyl groups of the polyol are substituted with a modifying group. The modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have a substituent. From the viewpoint of improving liquid repellency, the polyol modification may have a structure in which the polyol is modified with an alkyl group having 6 to 40 carbon atoms which may have a substituent (for example, an unsubstituted alkyl group having 6 to 40 carbon atoms).

[0036] (Optionally substituted monovalent hydrocarbon group) The hydrocarbon group used to modify the polyol of the modified polyol may be a monovalent hydrocarbon group which may have a substituent.

[0037] The hydrocarbon group may be a monovalent hydrocarbon group having 1 to 40 carbon atoms. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be branched, cyclic or linear, and is more preferably linear.

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

[0039] The hydrocarbon group may have a substituent, but is preferably unsubstituted. Examples of the substituent include -OR', -N(R')2, -COOR', and halogen atoms (wherein R' is independently a hydrogen atom or an organic group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms (e.g., a hydrocarbon group, particularly an aliphatic hydrocarbon group) in each occurrence). The substituent may or may not have active hydrogen. The number of the substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the hydrocarbon group having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, 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 (eg, 1) -OR' (particularly -OH) as a substituent (eg, other than at a terminal position).

[0040] (monovalent polysiloxane group) The polysiloxane group modified on the polyol of the polyol-modified product may be a monovalent polysiloxane group. The (monovalent) polysiloxane group, like the (monovalent) hydrocarbon group, can impart liquid repellency to the substrate.

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

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

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

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

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

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

[0047] a may be 3 or more, 5 or more, 10 or more, 30 or more, 50 or more, 100 or more, 500 or more, 1000 or more, 2000 or more, or 3000 or more, and is preferably 10 or more, 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.

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

[0049] In the polysiloxane group, R is a hydrocarbon group having 6 to 40 carbon atoms. s The amount of R s 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 the above.

[0050] In the polysiloxane group, R s The amount of R s and 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 above.

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

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

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

[0054] Examples of polysiloxane groups include: -[-Si(R s )2-O-] a -Si(R s )3 -L s1 -[-Si(R s )2-O-] a -Si(R s )3 -L s1 -OL s1 -[-Si(R s )2-O-] a -R s -L s1 -[-Si(R s )2-O-] a -Si(R s )3 -L s1 -OL s1 -[-Si(R s )2-O-] a -R s -L s1 -[-Si(R s )2-O-] a -Si(R s ) 3、 -L s1 -[-Si(R s )2-O-]a -R s [In the formula, R s is independently in each occurrence a hydrocarbon group or a reactive group having 1 to 40 carbon atoms, s has one or more reactive groups, R s 50 mol % or more of the total groups are methyl groups, L s1 is a hydrocarbon group having 1 to 20 carbon atoms, a is between 5 and 10,000. JPEG2025023980000001.jpg31109 [In the formula, a represents an integer of 0 to 150, b represents an integer of 1 to 150, (a+b) is 5 to 200, and n is an integer of 0 to 36.] etc.

[0055] (-YZ n ) In the present disclosure, modified polyols are those in which one or more of the hydroxy groups of the polyol has the formula: -YZ n [In the formula, Y is Y 1 and Y 2 is a 1+n valent group consisting of one or more selected from the group consisting of Y 1 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-, -NR'-, -C(OR')R'-, -C(OR')(-)2, -N(-)2 (wherein R' is independently in each occurrence a hydrogen atom or an organic group (e.g., a hydrocarbon group, particularly an aliphatic hydrocarbon group) having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms), Y 2 is a group consisting of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent aromatic hydrocarbon rings, and optionally substituted di- to tetravalent heterocycles, Z is a monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a monovalent polysiloxane group, n is an integer between 1 and 3. is substituted with a group represented by the following formula:

[0056] (Y) Y is Y 1 and Y 2 is a 1+n valent group consisting of one or more selected from the group consisting of Y 1 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-, -NR'-, -C(OR')R'-, -C(OR')(-)2, -N(-)2 (wherein R' is independently in each occurrence a hydrogen atom or an organic group (e.g., a hydrocarbon group, particularly an aliphatic hydrocarbon group) having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms), Y 2 is a group composed of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent aromatic hydrocarbon rings, and optionally substituted di- to tetravalent heterocycles.

[0057] n is the number of Zs bonded to Y, and may be an integer of 1 to 3. n may be 1 or more, 2 or more, or 3 or more, and may be 3 or less, 2 or less, or 1 or less, for example, 2 or less.

[0058] The molecular weight of Y may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more; 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.

[0059] ○ Y 1 Y 1 is a non-hydrocarbon linker.

[0060] Y 1 is a direct bond or a divalent or higher group. 1 The valence of Y may be 2 to 4, 2 to 3, or 2. 1 is preferably not only a direct bond.

[0061] Y 1 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.

[0062] Y 1 may be composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -S(=O)2-, -NR'-, -C(OR')R'-, and -C(OR')(-)2 (wherein R' is independently in each occurrence a hydrogen atom or an organic group (e.g., a hydrocarbon group, particularly an aliphatic hydrocarbon group) having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms). Y 1 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:

[0063] ○ Y 2 Y 2 is a linker of a hydrocarbon ring which may have a substituent, a hydrocarbon aromatic ring which may have a substituent, or a heterocycle which may have a substituent.

[0064] Y 2 Y may be a hydrocarbon group or a non-hydrocarbon group (including heteroatoms). 2 Y may be aliphatic or aromatic. 2 may be linear, branched or cyclic.

[0065] Y 2 is a divalent or higher group. Y 2 The valency of may be, for example, 2 to 4, 2 to 3, or 2.

[0066] Y 2 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; 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.

[0067] Y 2 is composed of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent aromatic hydrocarbon rings, and optionally substituted di- to tetravalent heterocycles.

[0068] The divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or straight chain hydrocarbon group. The divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The number of carbon atoms 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 4 or less, 3 or less, or 2.

[0069] The aliphatic hydrocarbon group may have a substituent. Examples of the substituent include -OR', -N(R')2, -COOR', and a halogen atom (wherein R' is, independently at each occurrence, a hydrogen atom or an organic group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms (e.g., a hydrocarbon group, particularly an aliphatic hydrocarbon group)). The substituent may or may not have active hydrogen. The number of the substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the aliphatic hydrocarbon group having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0070] Examples of divalent to tetravalent hydrocarbon aromatic rings include groups obtained by removing 2 to 4 hydrogen atoms from a hydrocarbon aromatic ring 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.

[0071] The aromatic hydrocarbon ring may have a substituent. Examples of the substituent include -R', -OR', -N(R')2, -COOR', and halogen atoms (wherein R' is independently a hydrogen atom or an organic group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms (e.g., a hydrocarbon group, particularly an aliphatic hydrocarbon group) in each occurrence). The substituent may or may not have active hydrogen. The number of the 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 aromatic hydrocarbon ring having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0072] The divalent to tetravalent heterocycle may be an aliphatic group or an aromatic group. Examples of the divalent to tetravalent heterocycle 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, and preferably 5 to 12. The valence of the heterocycle may be 2 or more, 3 or more, or 4, and may be 4 or less, 3 or less, or 2.

[0073] The heterocycle may have a substituent. Examples of the substituent include -R', -OR', -N(R')2, -COOR', and a halogen atom (wherein R' is, independently at each occurrence, a hydrogen atom or an organic group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms (e.g., a hydrocarbon group, particularly an aliphatic hydrocarbon group)). The substituent may or may not have active hydrogen. The number of the 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 heterocycle having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, for example, 65 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less.

[0074] Y 2 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.

[0075] Y 2 Examples of 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 an integer of 0 to 20, for example, 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle). etc.

[0076] (Example of Y) Examples of Y are described below. In the following, R' is independently in each occurrence a hydrogen atom or an organic group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) (e.g., a hydrocarbon group, particularly an aliphatic hydrocarbon group).

[0077] An example of Y is -Y when Y is bivalent. 1 -, -Y 1 -Y 2 -, -Y 1 -Y 2 -Y 1 -, -Y 1 -Y 2 -Y 1 -Y 2 -, -Y 2 -, -Y 2 -Y 1 -, -Y 2 -Y 1 -Y 2 -, -Y 2 -Y 1 -Y 2 -Y 1 --etc.

[0078] An example of Y is -Y when Y is trivalent. 1 (-)2, -Y 1 -Y 2 (-)2, -Y 1 -(Y 2 -)2, -Y 1 -Y 2 -Y 1 (-)2, -Y 1 -Y 2 (-Y 1 -)2, -Y 1 -(Y 2 -Y 1 -)2, -Y1 -Y 2 -Y 1 -Y 2 (-)2, -Y 1 -Y 2 -Y 1 -(Y 2 -) 2、 -Y 1 -Y 2 -(Y 1 -Y 2 -) 2、 -Y 1 -(Y 2 -Y 1 -Y 2 )2; -Y 2 (-)2, -Y 2 -Y 1 (-)2, -Y 2 -(Y 1 )2, -Y 2 -Y 1 -Y 2 (-)2, -Y 2 -Y 1 (-Y 2 )2, -Y 2 -(Y 1 -Y 2 )2, -Y 2 -Y 1 -Y 2 -Y 1 (-)2, -Y 2 -Y 1 -Y 2 -(Y 1 ) 2、 -Y 2 -Y 1 -(Y 2 -Y 1 ) 2、 -Y 2 -(Y 1 -Y 2 -Y 1 )2; etc. can be mentioned.

[0079] As an example of Y, when Y is tetravalent, -Y 1 (-)3, -Y 1 -Y 2 (-)3, -Y 1 -(Y 2 )3, -Y 1 -Y2 -Y 1 (-)3, -Y 1 -Y 2 (-Y 1 -)3, -Y 1 -(Y 2 -Y 1 -)3, -Y 1 -Y 2 -Y 1 -Y 2 (-)3, -Y 1 -Y 2 -Y 1 -(Y 2 -) 3、 -Y 1 -Y 2 -(Y 1 -Y 2 -) 3、 -Y 1 -(Y 2 -Y 1 -Y 2 -)3; -Y 2 (-)3, -Y 2 -Y 1 (-)3, -Y 2 -(Y 1 -)3, -Y 2 -Y 1 -Y 2 (-)3, -Y 2 -Y 1 (-Y 2 -)3, -Y 2 -(Y 1 -Y 2 -)3, -Y 2 -Y 1 -Y 2 -Y 1 (-)3, -Y 2 -Y 1 -Y 2 -(Y 1 -) 3、 -Y 2 -Y 1 -(Y 2 -Y 1 -) 3、 -Y 2 -(Y 1 -Y 2 -Y 1 -)3; include the following.

[0080] Preferred examples of Y include -Y 1 -, -Y 1 -Y 2 -, -Y 1 -Y 2 -Y 1 -, -Y 1 -Y 2 (-)2, -Y 2 -, -Y 2 -Y 1 -, -Y 2 -Y 1 -Y 2 -, -Y 2 -Y 1 (-)2, etc.

[0081] (Examples of preferred Y) Preferably, Y is -OY 11 -or -OY 11 -Y 21 -Y 12 - wherein each symbol represents independently at each occurrence: Y 11 is a direct bond, -C(=O)-, -C(=O)-NR'-, or -C(=S)-NR'-; Y 21 is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, Y 12 is -O-, -OC(=O)-, -OC(=O)-O-, -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO2-, -SO2NR'-, -C(OR')R'-, or -C(OR')(-)2. It may be.

[0082] Y 11 is a non-hydrocarbon linker, which is a direct bond or a divalent or higher group.

[0083] Y 11 The molecular weight may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less, and may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more.

[0084] Y 11 may be a direct bond, -C(=O)-, -C(=O)-NR'-, or -C(=S)-NR'-.

[0085] Y 21 is a divalent hydrocarbon linker which may have a substituent, and may be a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent.

[0086] Y 21 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; 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.

[0087] Here, the hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or straight chain hydrocarbon group, and may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The hydrocarbon group may have a substituent. Examples of the substituent include -OR', -N(R')2, -COOR', and a halogen atom (wherein R' is independently a hydrogen atom or an organic group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms (e.g., a hydrocarbon group, particularly an aliphatic hydrocarbon group) in each occurrence). The substituent may or may not have an active hydrogen. The number of the substituent 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, and 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.

[0088] Y 21 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 an integer of 0 to 20, for example, 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle). etc.

[0089] Y 12 may be -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO2-, -SO2NR'-, -C(OR')R'-, or -C(OR')(-)2.

[0090] (Z) Z is a monovalent hydrocarbon group or monovalent polysiloxane group having 1 to 40 carbon atoms which may have a substituent, and the explanations in the above (monovalent hydrocarbon group which may have a substituent) and (monovalent polysiloxane group) are incorporated herein. The number of carbon atoms in the hydrocarbon group is preferably 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, and preferably 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less. The hydrocarbon group may also contain an unsaturated bond, and the number of unsaturated bonds is preferably 4 or less, 2 or less, or 1. The substituent is preferably OH (hydroxy group).

[0091] [Other modifying groups] The hydroxyl group of the polyol is -YZ nExamples of modifying groups are anionic and / or cationic groups.

[0092] The anionic group may be a monomer having a carboxyl group, a sulfonic acid group, or a phosphoric acid group.

[0093] Salts of anionic groups include alkali metal salts, alkaline earth metal salts, or ammonium salts, such as methylammonium salts, ethanolammonium salts, and triethanolammonium salts.

[0094] The cationic group is an amino group, preferably a tertiary amino group and a quaternary amino group. In the tertiary amino group, the two groups bonded to the nitrogen atom are 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 (aryl group), or an araliphatic group having 7 to 25 carbon atoms (particularly an aralkyl group, for example, a benzyl group (C6H5-CH2-)). 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 (aryl group), or an araliphatic group having 7 to 25 carbon atoms (particularly an aralkyl group, for example, a benzyl group (C6H5-CH2-)). In the tertiary amino group and the quaternary amino group, the remaining group bonded to the nitrogen atom may have a carbon-carbon double bond. The cationic group may be in the form of a salt.

[0095] The cationic group that is a salt is a salt with an acid (organic acid or inorganic acid). Organic acids, for example, carboxylic acids having 1 to 20 carbon atoms (particularly, monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and stearic acid) are preferred.

[0096] [Method of producing modified polyol] The modified polyol may be prepared by reacting a modifying agent having a modifying group (or a precursor structure of the modifying group) with a hydroxy group of the polyol.

[0097] (Polyol) A polyol is a compound having two or more hydroxyl groups, and is a compound that is a raw material for a modified polyol. A polyol is a compound having two or more hydroxyl groups in the molecule. The polyol may be aliphatic or aromatic, but is preferably aliphatic.

[0098] 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.

[0099] When the polyol is a polymer, it may have a hydroxy group and an ether bond in the repeating structure of the monomer unit.

[0100] The polyol may be low molecular weight (e.g., weight average molecular weight less than 1000, 500 or less) and / or high molecular weight. The weight average molecular weight of the polyol may be 50 or more, 100 or more, 300 or more, 500 or more, 1000 or more, 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more, and may be 3000000 or less, 1000000 or less, 750000 or less, 500000 or less, 300000 or less, 100000 or less, 75000 or less, 500000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 10000 or less, 5000 or less, 30000 or less, 2000 or less, 1000 or less, or 500 or less.

[0101] 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.

[0102] The hydroxy group equivalent of the polyol may be 20 or more, 40 or more, 60 or more, 80 or more, 100 or more, 120 or more, 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 of the polyol is the value obtained by dividing the weight average molecular weight of the polyol by the number of hydroxyl groups.

[0103] 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.

[0104] Examples of monosaccharides include glucose, fructose, galactose, xylose, and the like.

[0105] Examples of oligosaccharides include sucrose, cycloamylose, cyclodextrin, maltose, trehalose, lactose, and sucralose.

[0106] Examples of sugar alcohols (reducing sugars) include sorbitol, maltitol, erythritol, isomalt, lactitol, mannitol, xylitol, sorbitan, lactitol, and the like.

[0107] 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.

[0108] Examples of hydroxy acids include ascorbic acid, kojic acid, quinic acid, chlorogenic acid, gluconic acid, and the like.

[0109] Examples of amino acids include glucosamine.

[0110] Examples of vitamins include ascorbic acid and inositol.

[0111] Examples of flavonols include catechin, quercetin, and anthocyanin.

[0112] Examples of hydroxyhydrocarbons include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, glycerin, trimethylolpropane, trimethylolethane, etc. Hydroxyhydrocarbons are hydrocarbons having a hydroxy group and may be aromatic or aliphatic, but are preferably aliphatic. Hydroxyhydrocarbons may also refer to hydroxyhydrocarbons other than compounds included in other groups such as polysaccharides (other hydroxyhydrocarbons).

[0113] 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.

[0114] 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 a hydroxyl group with two or more functional groups. Examples of initiators include propylene glycol, polypropylene glycol, ethylene glycol, polyethylene glycol, glycerin, polyglycerin, trimethylolpropane, triethanolamine, pentaerythritol, ethylenediamine, aromatic diamine, diethylenetriamine, sorbitol, and sucrose. Examples of alkylene oxides include ethylene oxide and propylene oxide. Polyether polyols obtained by addition polymerization of an alkylene oxide to the above initiators are also called polyoxyalkylene polyols or oxyalkylene derivatives of polyols. Representative examples of polyether polyols include polyoxypropylene triols obtained by addition polymerization of propylene oxide to glycerin, and polyoxypropylene polyglyceryl ethers obtained by addition polymerization of propylene oxide to polyglycerin.

[0115] 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.

[0116] Examples of polyester polyols may be compounds obtained by dehydration condensation of a compound having a carboxyl group with two or more functional groups and a compound having a hydroxyl group with two or more functional groups. Examples of compounds having a carboxyl group with two or more functional 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 a hydroxyl group with two or more functional groups include ethylene glycol, propylene glycol, propanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and polymers thereof.

[0117] (Modifier) The modifying agent is a compound that is reactive with a polyol and is preferably a compound having the above-mentioned monovalent hydrocarbon group having 1 to 40 carbon atoms, which may have a substituent, or a monovalent polysiloxane group.

[0118] Examples of modifying agents are as follows: Acid halide G(O=)CZ Acid anhydride O(C(=O)-Z)2 Carboxylic acid HO(O=)CZ Isocyanate O=C=NZ Thioisocyanate S=C=NZ Epoxy (CH2OCH)CH2O-Z Halide GZ Amine H2N-Z Hydroxy HO-Z [In the formula, Z is as described above, and G is a halogen atom (e.g., F, Cl, Br, or I).]

[0119] Z in the structure of the modifying agent described above may be replaced with any group constituting a modifying group. For example, Z may be a group having a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group, which may have a substituent. For example, Z may be -YZ n It is also possible to use the following.

[0120] The modified polyol may be synthesized by reacting a polyol with a modifying agent. For example, a modified polyol can be synthesized by reacting a modifying agent that is 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 that is a halide or an epoxy compound with a hydroxy group of a polyol to form an ether bond. Those skilled in the art can appropriately design the reaction conditions between the polyol and the modifying agent, such as using a catalyst (e.g., an acid catalyst or a base catalyst) or using a condensing agent, depending on the target product.

[0121] [Amine Modified Compounds] The amine-modified material of the present disclosure can be attached to a substrate to impart liquid repellency to the substrate.

[0122] [Characteristics, etc.] Due to its structure, the amine-modified compound in the present disclosure has excellent dispersibility in liquid media, and the repellent of the present disclosure can have stable performance. Repellents that use polymer-type compounds as active ingredients tend to have a wide molecular weight distribution and contain relatively large amounts of impurity components. On the other hand, the amine-modified compound can be made into a low molecular weight compound, and the molecular weight distribution can be narrowed (unitized), which can result in good performance.

[0123] The HD (n-hexadecane) contact angle of the amine-modified product may be 10° or more, 15° or more, 25° or more, 35° or more, 55° or more, 55° or more, or 65° or more, and may be 100° or less, 90° or less, or 75° or less. When the amine-modified product has an HD contact angle equal to or greater than the above lower limit, the substrate can be imparted with good liquid repellency (particularly oil repellency). The HD contact angle is the static contact angle of the amine-modified product with respect to a spin-coated film as shown in the examples, 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.

[0124] The water contact angle of the amine-modified product 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 amine-modified product 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 amine-modified product with respect to the spin-coated film as shown in the examples, 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.

[0125] The amine-modified product is preferably a compound having carbon of bio-based origin. The bio-based degree is measured in accordance with ASTM D6866. The bio-based degree 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 bio-based degree means that the amount of fossil resource-based materials, such as petroleum, used is small, and from this perspective, the higher the bio-based degree of the amine-modified product, the more preferable it is.

[0126] The biodegradability of the amine-modified product after 180 days is preferably 5% or more. Since the environmental load is reduced, the higher the biodegradability, the more preferable. The biodegradability of the amine-modified product 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 60% or more, more preferably 70% or more, even more preferably 80% or more, and most preferably 90% or more. The biodegradability of the amine-modified product after 60 days is preferably 5% or more. Since the environmental load is reduced, the higher the biodegradability, the more preferable. The biodegradability of the amine-modified product 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 50% or more, more preferably 60% or more. Such biodegradability may be the biodegradability defined in JIS K 6953-1 or ASTM D6400.

[0127] The melting point of the amine modified product may be 30° C. or more, 40° C. or more, 60° C. or more, 80° C. or more, 100° C. or more, or 120° C. or more, preferably 40° C. or more, and may be 200° C. or less, 150° C. or less, 130° C. or less, 120° C. or less, 110° C. or less, 100° C. or less, 80° C. or less, or 50° C. or less. The amine modified product may have no melting point.

[0128] [Structure etc.] The amine-modified product 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 amine-modified product does not contain these fluorine-containing groups, it can impart liquid repellency to the substrate.

[0129] The molecular weight of the amine modification 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.

[0130] The amine modified in the present disclosure may not have an active hydrogen-containing group. Examples of the active hydrogen-containing group include an amino group (an amino group that is not adjacent to a carbonyl group, such as a primary or secondary amino group), a hydroxyl group, and a carboxyl group. In particular, the amine modified in the present disclosure may not have a primary or secondary amino group that is not adjacent to a carbonyl group.

[0131] The amine-modified product in the present disclosure may be a polyamide having multiple amide groups, for example, a polyamide in which an amine (a raw amine compound, such as a polyamine) is modified with multiple modifying groups (such as Z, which will be described below) via amide groups. Here, the amide may include an amide moiety contained in a urethane group, a urea group, an imide, etc.

[0132] The amine modified product may be a compound obtained by modifying an amine (raw amine compound) with a monovalent hydrocarbon group having 1 to 40 carbon atoms, which may have a substituent, or a monovalent polysiloxane group.

[0133] In the amine-modified product, one or more amino groups of the amine are substituted with a modifying group. The modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have a substituent. From the viewpoint of improving liquid repellency, the amine-modified product may have a structure in which an amine is modified with an alkyl group having 6 to 40 carbon atoms.

[0134] (Optionally substituted monovalent hydrocarbon group) The hydrocarbon group modified on the amine of the amine-modified product may be a monovalent hydrocarbon group which may have a substituent.

[0135] The hydrocarbon group may be a monovalent hydrocarbon group having 1 to 40 carbon atoms. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and 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.

[0136] The number of carbon atoms in the hydrocarbon group may be 1 or more, 3 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, and is preferably 6 or more, 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, and is preferably 30 or less, 25 or less, or 20 or less.

[0137] The hydrocarbon group may have a substituent, but is preferably unsubstituted. Examples of the substituent include -OR', -N(R')2, -COOR', and halogen atoms (wherein R' is independently a hydrogen atom or an organic group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms (e.g., a hydrocarbon group, particularly an aliphatic hydrocarbon group) in each occurrence). The substituent may or may not have active hydrogen. The number of the substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the hydrocarbon group having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, 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 (eg, 1) -OR' (particularly -OH) as a substituent (eg, other than at a terminal position).

[0138] (monovalent polysiloxane group) The polysiloxane group modified with the amine of the amine-modified product may be a monovalent polysiloxane group. The (monovalent) polysiloxane group, like the (monovalent) hydrocarbon group, can impart liquid repellency to the substrate.

[0139] 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:

[0140] R s is a hydrocarbon group having 1 to 40 carbon atoms or a reactive group.

[0141] Examples of the hydrocarbon group having 1 to 40 carbon atoms include hydrocarbon groups having 1 to 5 carbon atoms and hydrocarbon groups having 6 to 40 carbon atoms.

[0142] Examples of the hydrocarbon group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and other hydrocarbon groups having 1 to 5 carbon atoms (particularly an aliphatic hydrocarbon group, particularly an alkyl group such as a methyl group or an ethyl group, particularly a methyl group).

[0143] 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.

[0144] 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, hydrogen atoms directly bonded to silicon atoms, etc.). These functional groups may be directly bonded to silicon atoms, or may be bonded to organic groups directly bonded to silicon atoms. The organic groups may be hydrocarbon groups, such as alkylene groups or divalent aromatic groups. The hydrocarbon groups may have 2 to 12 carbon atoms, and alkylene groups preferably have 2 to 10 carbon atoms. Divalent aromatic groups preferably have 6 to 12 carbon atoms. The reactive groups may be groups selected from the group consisting of hydroxyl, epoxy rings, carboxyl, (meth)acrylic, and amino groups, and may be at least one selected from the group consisting of epoxy rings, hydroxyl, (meth)acrylic, and carboxyl groups.

[0145] a may be 3 or more, 5 or more, 10 or more, 30 or more, 50 or more, 100 or more, 500 or more, 1000 or more, 2000 or more, or 3000 or more, and is preferably 10 or more, 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.

[0146] In the polysiloxane group, R is a hydrocarbon group having 1 to 5 carbon atoms. s The amount of R s With respect to the total of R, 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. For example, R s Based on the total number of groups, 50 mol % or more may be methyl or ethyl groups (particularly methyl groups).

[0147] In the polysiloxane group, R is a hydrocarbon group having 6 to 40 carbon atoms. s The amount of Rs 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 the above.

[0148] In the polysiloxane group, R s The amount of R s and 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 above.

[0149] R s The groups may be introduced randomly or in blocks, but are preferably introduced randomly.

[0150] The terminal structure of the polysiloxane group is not limited, but may be -OR s , -Si(R s )3, etc. s Examples of the reactive group are as described above, and may be, for example, at least one selected from the group consisting of an epoxy ring, a hydroxy group, a (meth)acrylic group, and a carboxyl group.

[0151] The polysiloxane group may have a linker, and the amine 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.

[0152] Examples of polysiloxane groups include: -[-Si(R s )2-O-] a -Si(R s )3 -L s1 -[-Si(R s )2-O-] a -Si(Rs )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, s has one or more reactive groups, R s 50 mol % or more of the total groups are methyl groups, L s1 is a hydrocarbon group having 1 to 20 carbon atoms, a is between 5 and 10,000. TIFF2025023980000002.tif31109 [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.

[0153] For example, the amine modification is an amine backbone, and The formula: -XZ n [In the formula, X is a direct bond or a 1+n valent group; Z is a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group which may have a substituent, n is an integer between 1 and 3. has one or more groups represented by At least one -XZ n is bonded to a nitrogen atom of the amine skeleton.

[0154] (amine skeleton) The amine modified product in the present disclosure has an amine skeleton. The amine skeleton has one or more amino groups having a predetermined number of bonds (valences) 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 means a group selected from the group consisting of -NH2, -NH-, and -N(-)2, and also includes an amino group adjacent to a carbonyl group contained in an amide group, a urethane group, a urea group, an imide group, etc. Note that the amine skeleton may be an aliphatic group or an aromatic group having one or more amino groups, and does not exclude the presence of heteroatoms other than nitrogen.

[0155] 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.

[0156] 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, and particularly 30 or less.

[0157] The amine skeleton has one or more amino groups. The amino group is a monovalent to trivalent amino group, and is one or more groups selected from the group consisting of -NH2, -NH-, and -N(-)2. The number of amino groups in the amine skeleton may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, and is preferably 2 or more, 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.

[0158] 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 (for example, saturated). Here, the hydrocarbon group may be interrupted by an oxygen atom and / or a sulfur atom, or may be composed of only carbon atoms, nitrogen atoms, and hydrogen atoms. The hydrocarbon group may be a hydrocarbon group that may be interrupted by an oxygen atom and / or a sulfur atom (for example, a chain-like saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 hydrocarbon aromatic rings), or may be a general hydrocarbon group (for example, a chain-like saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 hydrocarbon aromatic rings). When the hydrocarbon group is interrupted by an oxygen atom and / or a sulfur atom, it 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.

[0159] The amine skeleton may be composed of a monovalent to trivalent amino group and a chain-like saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group which may be interrupted by an oxygen atom and / or a sulfur atom.

[0160] 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.

[0161] (-XZ n ) The amine modification of the present disclosure has the formula: -XZ n [In the formula, X is a direct bond or a 1+n valent group; Z is a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group which may have a substituent, n is an integer between 1 and 3. has one or more groups represented by At least one -XZ n is bonded to a nitrogen atom of the amine skeleton.

[0162] Amine modification has -XZ n The number may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, and is preferably 2 or more, 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.

[0163] At least one -XZ in the amine modification n is bonded to the nitrogen atom of the amine skeleton. All -XZ in the amine modification n Among the number of -XZ bonded to the nitrogen atom of the amine skeleton, n The ratio of the number of -XZ which is 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 75% or less, 50% or less, or 25% or less. n binds to another group (e.g., a hydrocarbon group) on the amine skeleton.

[0164] (X) X is a direct bond or a 1+n valent group, preferably a 1+n valent group. X functions as a linker connecting the amine skeleton and n Z's.

[0165] n is the number of Z's bonded to X, and may be an integer of 1 to 3. 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.

[0166] X may be an aliphatic group (unsaturated aliphatic group or saturated aliphatic group) or an aromatic group.

[0167] The molecular weight of X 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.

[0168] X may have a carbonyl group. X may have one or more selected from the group consisting of an amide group, a urea group, a urethane group, and an imide, or X may form one or more selected from the group consisting of an amide group, a urea group, a urethane group, and an imide together with the amino group in the amine skeleton. Examples of such amide groups, urea groups, urethane groups, and imides 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).] X is preferably bonded to a nitrogen atom in the amine skeleton via a -(C=O)- group.

[0169] X is a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, -C(OR')R'-, -C(OR')(-)2, -N(-)2, a di- to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a di- to tetravalent hydrocarbon aromatic ring, or a di- to tetravalent heterocycle. [In the formula, R' is a hydrogen atom or an organic group (e.g., a hydrocarbon group, particularly an aliphatic 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:

[0170] X is X 1 and X 2 is a 1+n valent group consisting of one or more selected from the group consisting of X 1 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-, -NR'-, -C(OR')R'-, -C(OR')(-)2, -N(-)2 (wherein R' is independently in each occurrence a hydrogen atom or an organic group (e.g., a hydrocarbon group, particularly an aliphatic hydrocarbon group) having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms), X 2 is a group consisting of one or more selected from the group consisting of di- to tetravalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms, di- to tetravalent aromatic hydrocarbon rings, and di- to tetravalent heterocycles, In the present specification, the left side of the group described as X is bonded to the amine skeleton, and the right side is bonded to Z.

[0171] 〇X 1 X 1 is a non-hydrocarbon linker.

[0172] X 1 is a direct bond or a divalent or higher group. X 1 The valence of X may be 2 to 4, 2 to 3, or 2. 1 is preferably not only a direct bond.

[0173] X 1The 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.

[0174] X 1 may be composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, -C(OR')R'-, -C(OR')(-)2, and -N(-)2 (wherein R' is independently in each occurrence a hydrogen atom or an organic group (e.g., a hydrocarbon group, particularly an aliphatic hydrocarbon group) having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms). X 1 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 an organic group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) (e.g., a hydrocarbon group, particularly an aliphatic hydrocarbon group).] In addition, X 1 is bonded to a nitrogen atom of the amine skeleton, the nitrogen atom is considered to be part of the amine skeleton (amino group).

[0175] X 2 X 2 is a linker of a hydrocarbon ring which may have a substituent, a hydrocarbon aromatic ring which may have a substituent, or a heterocycle which may have a substituent.

[0176] X 2 X may be a hydrocarbon group or a non-hydrocarbon group (including heteroatoms). 2 X may be aliphatic or aromatic. 2 may be linear, branched or cyclic.

[0177] X 2 is a divalent or higher group. X 2 The valency of may be, for example, 2 to 4, 2 to 3, or 2.

[0178] X 2 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; 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.

[0179] X 2 is composed of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent aromatic hydrocarbon rings, and optionally substituted di- to tetravalent heterocycles.

[0180] The divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or straight chain hydrocarbon group. The divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The number of carbon atoms 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 4 or less, 3 or less, or 2.

[0181] The aliphatic hydrocarbon group may have a substituent. Examples of the substituent include -OR', -N(R')2, -COOR', and a halogen atom (wherein R' is, independently at each occurrence, a hydrogen atom or an organic group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms (e.g., a hydrocarbon group, particularly an aliphatic hydrocarbon group)). The substituent may or may not have active hydrogen. The number of the substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the aliphatic hydrocarbon group having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0182] Examples of divalent to tetravalent hydrocarbon aromatic rings include groups obtained by removing 2 to 4 hydrogen atoms from a hydrocarbon aromatic ring 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.

[0183] The aromatic hydrocarbon ring may have a substituent. Examples of the substituent include -R', -OR', -N(R')2, -COOR', and halogen atoms (wherein R' is independently a hydrogen atom or an organic group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms (e.g., a hydrocarbon group, particularly an aliphatic hydrocarbon group) in each occurrence). The substituent may or may not have active hydrogen. The number of the 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 aromatic hydrocarbon ring having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0184] The divalent to tetravalent heterocycle may be an aliphatic group or an aromatic group. Examples of the divalent to tetravalent heterocycle 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, and preferably 5 to 12. The valence of the heterocycle may be 2 or more, 3 or more, or 4, and may be 4 or less, 3 or less, or 2.

[0185] The heterocycle may have a substituent. Examples of the substituent include -R', -OR', -N(R')2, -COOR', and a halogen atom (wherein R' is independently a hydrogen atom or an organic group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms (e.g., a hydrocarbon group, particularly an aliphatic hydrocarbon group) in each occurrence). The substituent may or may not have an active hydrogen. The number of the substituent may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In a heterocycle having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, for example, 65 mol% or more, and the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less.

[0186] X 2 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.

[0187] X 2 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 an integer of 0 to 20, for example, 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle). etc.

[0188] Example of X Examples of X are described below. In the following, R' is independently in each occurrence a hydrogen atom or an organic group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) (e.g., a hydrocarbon group, particularly an aliphatic hydrocarbon group).

[0189] An example of X is -X when X is bivalent. 1 -, -X 1 -X 2 -, -X 1 -X 2 -X 1 -, -X 1 -X 2 -X 1 -X 2 -, -X 2 -, -X 2 -X 1 -, -X 2 -X 1 -X 2 -, -X 2 -X 1 -X 2 -X 1 -, etc.

[0190] An example of X is -X when X is trivalent. 1 (-)2, -X 1 -X 2 (-)2, -X 1 -(X 2 -)2, -X 1 -X 2 -X 1 (-)2, -X 1 -X 2 (-X 1 -)2, -X 1 -(X 2 -X 1 -)2, -X1 -X 2 -X 1 -X 2 (-)2, -X 1 -X 2 -X 1 -(X 2 -) 2、 -X 1 -X 2 -(X 1 -X 2 -) 2、 -X 1 -(X 2 -X 1 -X 2 -)2; -X 2 (-)2, -X 2 -X 1 (-)2, -X 2 -(X 1 -)2, -X 2 -X 1 -X 2 (-)2, -X 2 -X 1 (-X 2 -)2, -X 2 -(X 1 -X 2 -)2, -X 2 -X 1 -X 2 -X 1 (-)2, -X 2 -X 1 -X 2 -(X 1 -) 2、 -X 2 -X 1 -(X 2 -X 1 -) 2、 -X 2 -(X 1 -X 2 -X 1 -)2 etc.

[0191] An example of X is -X when X is tetravalent. 1 (-)3, -X 1 -X 2 (-)3, -X 1 -(X 2 -)3, -X 1 -X 2 -X1 (-)3, -X 1 -X 2 (-X 1 -)3, -X 1 -(X 2 -X 1 -)3, -X 1 -X 2 -X 1 -X 2 (-)3, -X 1 -X 2 -X 1 -(X 2 -) 3、 -X 1 -X 2 -(X 1 -X 2 -) 3、 -X 1 -(X 2 -X 1 -X 2 -)3; -X 2 (-)3, -X 2 -X 1 (-)3, -X 2 -(X 1 -)3, -X 2 -X 1 -X 2 (-)3, -X 2 -X 1 (-X 2 -)3, -X 2 -(X 1 -X 2 -)3, -X 2 -X 1 -X 2 -X 1 (-)3, -X 2 -X 1 -X 2 -(X 1 -) 3、 -X 2 -X 1 -(X 2 -X 1 -) 3、 -X 2 -(X 1 -X 2 -X 1 -)3; etc.

[0192] Preferred examples of X include -X 1 -, -X 1 -X 2 -, -X 1 -X 2 -X 1 -, -X 1 -X 2 (-)2, -X 2 -, -X 2 -X 1 -, -X 2 -X 1 -X 2 -, -X 2 -X 1 (-)2, In the amine modified product, it is preferred that one or more Xs have a -(C=O)- group at the terminal on the amine skeleton side and are bonded to a nitrogen atom in the amine skeleton.

[0193] X is preferably -X 1 -, -X 1 -X 2 -, -X 1 -X 2 -X 1 -, -X 1 -X 2 (-)2, -X 2 -, -X 2 -X 1 -, -X 2 -X 1 -X 2 -, -X 2 -X 1 (-)2, [In the formula, X 1 but, independently for 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 an organic group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) (e.g., a hydrocarbon group, particularly an aliphatic hydrocarbon group).) and X 2 is a divalent to tetravalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, or a divalent aromatic group (for example, a divalent phenyl group, a divalent triazole group). This makes it possible to impart good liquid repellency to the substrate.

[0194] Further specific examples of X include: *-(C=O)- -O-(C=O)-NR'- [In the formula, * means bonding to a nitrogen atom of an amine skeleton, R' is a hydrogen atom or an organic group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) (e.g., a hydrocarbon group, particularly an aliphatic hydrocarbon group).] etc.

[0195] (Z) Z is a monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a monovalent polysiloxane group, and the above descriptions of (monovalent hydrocarbon group which may have a substituent) and (monovalent polysiloxane group) are incorporated herein.

[0196] [Examples of amine modifications] (Amine modification example 1) Examples of amine modifications include those of the formula: N(-XZ n ) p (-H) q -L 1 -[N(-XZ n ) r (-H) s -L 1 -] t -N(-XZn ) p (-H) q [In the formula, X is independently in each occurrence a direct bond or a group having a valence of 1+n; Z is independently in each occurrence a linear or branched monovalent hydrocarbon group having from 6 to 40 carbon atoms which may have a substituent; L 1 represents, 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, independently in each occurrence, is an integer between 1 and 3, inclusive; p, in each occurrence, is an integer greater than or equal to 0 and less than or equal to 2; q, independently in each occurrence, is an integer greater than or equal to 0 and less than or equal to 2; p+q is the sum of each N(-XZ 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(-XZ n ) r (-H) s In, 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. The compound represented by the following formula (amine modified example 1) is exemplified.

[0197] In the amine modification example 1, the details of X, Z, and n are as described above.

[0198] In the amine modification example 1, L 1 L is a divalent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms, which may be interrupted by oxygen atoms and / or sulfur atoms, and may be a cyclic, branched, or straight-chain hydrocarbon group, and is preferably a straight-chain hydrocarbon group or an aromatic hydrocarbon. 1The hydrocarbon group in the above description of the [amine skeleton] may be used as L, and 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. 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 aromatic hydrocarbon rings. 1 is preferably a cyclic group having both a ring (e.g., an aromatic ring) and a chain structure (e.g., a straight-chain 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.

[0199] In the amine modification example 1, p, in each occurrence, is independently an integer between 0 and 2, inclusive; q, in each occurrence, is independently an integer between 0 and 2, inclusive; and p+q is the sum of each N(-XZ n ) p (-H) q In the formula, p is 2. Preferably, p, independently at each occurrence, may be 1 or more, for example 2.

[0200] In the amine modification example 1, r is independently at each occurrence 0 or 1, s is independently at each occurrence 0 or 1, and r+s is independently at each occurrence 0 or 1. n ) r (-H) s In the formula, p is 1. Preferably, p, independently at each occurrence, may be 1 or more, for example 2.

[0201] The sum of all p's and all r's is 1 or greater, i.e., the exemplary amine modification 1 is one or more -XZ nThe sum of all p's and all r's may be 1 or more, 3 or more, 5 or more, 7 or more, 9 or more, 12 or more (the sum of all q's and all s's may be 0), or may be 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, or 4 or less.

[0202] In the 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, preferably 0 or more or 2 or more, and t may be 8 or less, 6 or less, 4 or less, or 3 or less.

[0203] (Amine modification example 2) Other examples of amine modifications include those of the formula: N(-XZ n ) p (-H) q -L 2 (-XZ n ) u [In the formula, X is independently in each occurrence a direct bond or a group having a valence of 1+n; Z is independently in each occurrence a linear or branched monovalent hydrocarbon group having from 6 to 40 carbon atoms which may have a substituent; L 2 represents an aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms and a valence of 1+u, which may be interrupted by an oxygen atom and / or a sulfur atom, n, independently in each occurrence, is 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 1 or greater.] The compound represented by the following formula (amine modified example 2) is also included.

[0204] In the amine modification example 2, the details of X, Z and n are as described above.

[0205] In the amine modification example 2, L 2 is an aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms and a valence of 1+u, which may be interrupted by oxygen atoms and / or sulfur atoms, and may be a cyclic, branched, or straight-chain hydrocarbon group, and is preferably a straight-chain hydrocarbon group or an aromatic hydrocarbon. 2 The hydrocarbon group in the above description of the [amine skeleton] may be used as L, and the hydrocarbon group may be interrupted by 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 aromatic hydrocarbon rings. 2 is preferably a cyclic group having both a ring (e.g., an aromatic ring) and a chain structure (e.g., a straight-chain structure, ether oxygen, or thioether sulfur), and specific examples thereof include a 1,3-phenylenebisalkylene group, a 1,4-phenylenebisalkylene group, a diphenyletherdiyl group, and a diphenylthioetherdiyl group. 2 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.

[0206] In the amine modification example 2, p is an integer of 0 to 2, q is an integer of 0 to 2, and p+q is 2. Preferably, p may be 1 or more, for example 2.

[0207] In the amine modification example 2, u is an integer of 1 to 3. u is 1, 2, or 3, for example, 2 or 3.

[0208] In the amine modification example 2, the sum of p and u is 1 or more, i.e., the amine modification example 2 is one or more -XZ n The sum of p and u may be 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more (q may be 0), and may be 5 or less, 4 or less, 3 or less, or 2 or less.

[0209] (Specific examples) Specific examples of the amine-modified product include compounds represented by the following formula: In the following formula, the above explanations are incorporated for details of X, Z, and n.

[0210] JPEG2025023980000003.jpg2830

[0211] JPEG2025023980000004.jpg2347

[0212] JPEG2025023980000005.jpg2635

[0213] JPEG2025023980000006.jpg1837

[0214] JPEG2025023980000007.jpg1547

[0215] JPEG2025023980000008.jpg1746

[0216] JPEG2025023980000009.jpg1553

[0217] 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 amine containing an aromatic group. 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, icosapentaenoic acid amide compounds, and docosahexaenoic acid amide compounds.

[0218] [Method of producing amine modified compounds] Methods for producing amine modifications include, but are not limited to, a synthesis method in which various amines (raw amines) are reacted with a Z group-containing carboxylic acid, optionally in the presence of a condensing agent, and a synthesis method in which various amines are reacted with a Z group-containing carboxylic acid chloride, acid anhydride, isocyanate, etc. The condensing agent may be a known condensing agent, and examples of the condensing agent include DCC, EDCI, CDI, BOP, COMU, DMT-MM, DPPA, Py-Bop, etc.

[0219] (Amine (raw amine)) Examples of amines (raw amines) that are precursors of the amine skeleton include those that can form an amine skeleton, such as alkylamines such as methylamine, ethylamine, propylamine, butylamine, and dibutylamine; alkylene diamines 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-aminopropyl)ethyl]ether. 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 ethane, 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 compound such as allylamine.

[0220] [Composition of liquid repellent compound] The liquid repellent compound may be a polyol-modified compound or an amine-modified compound, or both may be used in combination. The amount of the polyol-modified 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, 70% by weight or more, 80% by weight or more, or 90% by weight, or 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 total amount of the polyol-modified compound and the amine-modified compound.

[0221] [Amount of liquid repellent compound] The amount of the liquid repellent compound in the repellent agent may be 0.01% by weight or more, 0.5% 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, and may be 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.

[0222] [Dispersant] The repellent of the present disclosure preferably includes a dispersant (eg, a cationic dispersant).

[0223] 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.

[0224] The dispersant preferably contains a cationic dispersant. The dispersant may be a cationic dispersant alone, or may be used in combination with other dispersants in addition to the cationic dispersant. Examples of combinations of dispersants include a combination of a cationic dispersant and a nonionic dispersant, a combination of a cationic dispersant and an anionic dispersant, a combination of a cationic dispersant and an amphoteric dispersant, a combination of a cationic dispersant and an inorganic dispersant, and the like, and preferably a combination of a cationic dispersant and a nonionic dispersant. The repellent may not contain a dispersant other than a cationic dispersant, such as an anionic dispersant and / or a nonionic dispersant (e.g., an anionic dispersant). The dispersant may contain a dispersant other than a fatty acid ester having an HLB value of 7 or more. For example, the dispersant may contain a fatty acid ester-based dispersant having an HLB value of less than 7, or may contain a dispersant other than a fatty acid ester.

[0225] As the dispersant, an organic dispersant and an inorganic dispersant may be used separately, or an organic dispersant and an inorganic dispersant may be used in combination.

[0226] 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 mean a surfactant.

[0227] The dispersant may be fluorine-free.

[0228] [Nonionic dispersant] The dispersant may include a nonionic dispersant. The nonionic dispersant may be a nonionic surfactant.

[0229] The nonionic dispersant may be a low molecular weight or a high molecular weight dispersant. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may be 100,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0230] Examples of nonionic dispersants include ethers, esters, ester ethers, alkanolamides, polyols and amine oxides.

[0231] An example of an ether is a compound having an oxyalkylene group (preferably a polyoxyethylene group).

[0232] An example of the ester is an ester of an alcohol and a fatty acid. An example of the alcohol is a monohydric to tridehydric (particularly dihydric to decahydric) alcohol (e.g., an 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.

[0233] An example of the 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 the alcohol is a monohydric to tridecahydric (particularly dihydric to decahydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 3 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.

[0234] 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, having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0235] The polyol may be a di- to penta-hydric alcohol having 10 to 30 carbon atoms. The amine oxide may be an oxide (eg, having 5 to 50 carbon atoms) of an amine (secondary amine or preferably tertiary amine).

[0236] 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.

[0237] 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.

[0238] 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, and the like. Among these, those in which the structure of the alkylene oxide adduct portion and the polyalkylene glycol portion is polyoxyethylene (POE) or polyoxypropylene (POP) or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred. Additionally, the nonionic dispersant need not contain aromatic groups.

[0239] The nonionic dispersant has the formula: R 1 O-(CH2CH2O) p -(R 2 O) q -R 3 [In the formula, R 1is an alkyl group having 1 to 22 carbon atoms or an alkenyl group or acyl group having 2 to 22 carbon atoms, R 2 each is independently the same or different and is an alkylene group 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 equal to or greater than 2, q is a number equal to or greater than 0. The compound may be represented by the formula:

[0240] R 1 R preferably has 8 to 20 carbon atoms, particularly preferably 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 are a propylene group and a butylene group. In the nonionic dispersant, p may be a number of 3 or more (for example, 5 to 200). q may be a number of 2 or more (for example, 5 to 200). That is, -(R 2 O) q may form a polyoxyalkylene chain. The nonionic dispersant may be a polyoxyethylene alkylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) in the center. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, and a styrene chain, and among these, an oxypropylene chain is preferred.

[0241] 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.

[0242] The proportion of the polyoxyethylene block may 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.

[0243] [Cationic dispersants] 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.

[0244] The cationic dispersant may be a low molecular weight type (e.g., molecular weight of 2000 or less, particularly 10000 or less) or a polymer type (e.g., molecular weight of 2000 or more). The molecular weight of the cationic dispersant may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may be 1000000 or less, 750000 or less, 500000 or less, 250000 or less, 100000 or less, 50000 or less, 10000 or less, 7500 or less, 5000 or less, 25000 or less, 750 or less, or 250 or less.

[0245] The cationic dispersant may be aliphatic or aromatic, and may be, for example, an ammonium salt (e.g., a quaternary ammonium salt). 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 imidazoline; quaternary ammonium salt-type dispersants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, and benzethonium chloride; and polymer-type cationic dispersants such as polyquaternium-1 to 47.

[0246] 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 24Specific examples of X are alkyl groups (e.g., methyl, butyl, stearyl, and palmityl groups). Specific examples of X are halogens (e.g., chlorine) and acids (e.g., hydrochloric acid and acetic acid). The cationic dispersant may be a monoalkyltrimethylammonium salt (alkyl having 4 to 40 carbon atoms).

[0247] 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 ) linear and / or branched aliphatic (saturated and / or unsaturated) groups, R 2 is H, a C1-4 alkyl group, a benzyl group, or a polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (particularly 2, particularly 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 sulfonic acid salt; 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.

[0248] 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.

[0249] The polymeric cationic dispersant may be any of various polymers (e.g., polyquaternium-1 to 47) having a cationic group (e.g., ammonium group, quaternary ammonium group). Examples of the polymeric cationic dispersant include cationic starch, cationic cellulose (e.g., O-(2-hydroxy-3-(trimethylammonio)propyl hydroxyethyl cellulose chloride), cationic guar gum, cationic xanthan gum, chitosan, and other cationic natural products (particularly cationic sugars); aziridine, vinylimidazole, aminoalkyl methacrylate, N,N,N',N'-tetramethyl-2-butene-1,4-diamine, quaternary dimethylammonium ethyl methacrylic acid, diallyldimethylammonium chloride, dimethylaminopropylamine, quaternary vinylimidazole, and other cationic group-containing monomer polymers.

[0250] [Anionic dispersants] The dispersant may comprise an anionic dispersant. The anionic dispersant may be an anionic surfactant. The dispersant may be free of an anionic dispersant.

[0251] The anionic dispersant may be a low molecular weight or a high molecular weight. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may be 100,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0252] 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 fatty acid salts, N-acylamino acid type dispersants, phosphoric acid mono- or diester type dispersants, and sulfosuccinic acid esters.

[0253] [Amphoteric dispersant] The dispersant may comprise an amphoteric dispersant, which may be an amphoteric surfactant.

[0254] The amphoteric dispersant may be a low molecular weight or a high molecular weight dispersant. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may be 100,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0255] Examples of amphoteric dispersants include alanines, imidazolinium betaines, amido betaines, and betaine acetate. Specific examples include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylamino acetate betaine, and fatty acid amidopropyl dimethylamino acetate betaine.

[0256] [Inorganic dispersant] The dispersant may comprise an inorganic dispersant.

[0257] 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 a hydrophilic particle.

[0258] 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.

[0259] [Amount of dispersant] The amount of the dispersant may be, relative to 100 parts by weight of the liquid repellent compound, 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, 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.

[0260] [Liquid medium] The repellent in 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 may be a dispersion or a solution. The repellent in the present disclosure may be a water-dispersed type and may include at least water.

[0261] Examples of the organic solvent include esters (e.g., esters having 2 to 40 carbon atoms, specifically, ethyl acetate, butyl acetate), ketones (e.g., ketones having 2 to 40 carbon atoms, specifically, methyl ethyl ketone, diisobutyl ketone), alcohols (e.g., alcohols having 1 to 40 carbon atoms, specifically, isopropyl alcohol), aromatic solvents (e.g., toluene and xylene), and petroleum solvents (e.g., alkanes having 5 to 10 carbon atoms, specifically, naphtha, kerosene). The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent may contain a compound having at least one hydroxyl group (e.g., alcohol, polyols such as glycol-based solvents, ethers of polyols (e.g., monoethers), etc.). These may be used alone or in combination of two or more.

[0262] [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.

[0263] 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.

[0264] 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, 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.

[0265] 〔silicone〕 The repellent in the present disclosure may contain silicone (polyorganosiloxane). By containing silicone, it is possible to obtain good texture and durability in addition to good liquid repellency.

[0266] As the silicone, known silicones can be used, and examples of silicones include polydimethylsiloxane and modified silicones (amino-modified, epoxy-modified silicone, carboxy-modified silicone, methylhydrogen silicone, etc.). The silicone may be a silicone wax having wax-like properties. These may be used alone or in combination of two or more.

[0267] The weight average molecular weight of the silicone may be 1,000 or more, 10,000 or more, or 50,000 or more, and may be 500,000 or less, 2,500,000 or less, 100,000 or less, or 50,000 or less.

[0268] [Amount of silicone] The amount of silicone may be, relative to 100 parts by weight of the liquid repellent compound, 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, 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.

[0269] 〔wax〕 The repellent in the present disclosure may contain a wax. By containing a wax, it is possible to impart good liquid repellency to the substrate.

[0270] Examples of waxes include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin wax (polyethylene wax, polypropylene wax, etc.), oxidized polyolefin wax, silicone wax, animal and vegetable wax, mineral wax, etc. Paraffin wax is preferred. Specific examples of compounds constituting the wax include normal alkanes (e.g., tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane), and normal alkenes (e.g., 1-eicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane). The carbon number of the compound constituting the wax is preferably 20 to 60, for example, 25 to 45. The molecular weight of the wax may be from 200 to 2000, for example, from 250 to 1500, or from 300 to 1000. These may be used alone or in combination of two or more.

[0271] The melting point of the wax may be 50° C. or higher, 55° C. or higher, 60° C. or higher, 65° C. or higher, or 70° C. or higher, preferably 55° C. or higher, more preferably 60° C. or higher. The melting point of the wax is measured in accordance with JIS K 2235-1991.

[0272] [Amount of wax] The amount of wax may be, relative to 100 parts by weight of the liquid repellent compound, 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, 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.

[0273] [Organic acid] The repellent of the present disclosure may contain an organic acid. As the organic acid, a known one may be used. As the organic acid, carboxylic acid, sulfonic acid, sulfinic acid, etc. are preferably mentioned, and carboxylic acid is particularly preferable. As the carboxylic acid, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid, etc. are mentioned, and formic acid or acetic acid is particularly preferable. In the present disclosure, the organic acid may be used alone or in combination of two or more kinds. For example, formic acid and acetic acid may be used in combination.

[0274] [Amount of organic acid] The amount of the organic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, 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 the 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).

[0275] [Hardening agent] The repellent of the present disclosure may include a curing agent (an active hydrogen reactive compound or an active hydrogen containing compound).

[0276] The curing agent (crosslinking agent) in the repellent agent can effectively cure the liquid repellent compound. The curing agent may be an active hydrogen reactive compound or an active hydrogen-containing compound that reacts with the active hydrogen or active hydrogen reactive group of the liquid repellent compound. Examples of the active hydrogen reactive compound are isocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds, and hydrazide compounds. Examples of the active hydrogen-containing compound are hydroxyl group-containing compounds, amino group-containing compounds, carboxyl group-containing compounds, ketone group-containing compounds, hydrazide compounds, and melamine compounds.

[0277] The curing agent may include an isocyanate compound. The isocyanate compound may be a polyisocyanate compound. The polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound acts as a crosslinking agent. Examples of the polyisocyanate compound include aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates. The isocyanate compound may be a blocked isocyanate compound (e.g., a blocked polyisocyanate compound). The blocked isocyanate compound is a compound in which the isocyanate group of the isocyanate compound is masked with a blocking agent to suppress the reaction.

[0278] 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-di ... 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, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane, etc. These may be used alone or in combination of two or more.

[0279] 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.

[0280] Examples of the araliphatic polyisocyanate are araliphatic diisocyanate and araliphatic triisocyanate.Specific examples of the araliphatic polyisocyanate are 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethylxylylene diisocyanate) or a mixture thereof, and 1,3,5-triisocyanatomethylbenzene.These may be used alone or in combination of two or more.

[0281] Examples of aromatic polyisocyanates are aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates are 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.

[0282] Examples of the polyisocyanate derivatives include various derivatives of the above-mentioned polyisocyanate compounds, such as dimers, trimers, biurets, allophanates, carbodiimides, uretdione, uretoimine, isocyanurates, iminooxadiazinedione, etc. These may be used alone or in combination of two or more.

[0283] 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 the polyisocyanate compound is blocked with a blocking agent. It is preferable to use a blocked polyisocyanate compound because it is relatively stable even in a solution and can be used in the same solution as the repellent.

[0284] The blocking agent blocks free isocyanate groups. When the blocked polyisocyanate compound is heated to, for example, 100°C or higher, for example, 130°C or higher, the isocyanate group is regenerated and can easily react with the hydroxyl group. Examples of the blocking agent include phenol-based compounds, lactam-based compounds, aliphatic alcohol-based compounds, and oxime-based compounds. The polyisocyanate compounds can be used alone or in combination of two or more kinds.

[0285] 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. An example of the chloromethyl group-containing compound is 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.

[0286] Specific examples of the ketone group-containing compound include (poly)diacetone acrylamide and diacetone alcohol. Specific examples of the hydrazide compound include hydrazine, carbohydrazide, adipic acid hydrazide, and the like. Specific examples of the melamine compound include melamine resins and methyl etherified melamine resins.

[0287] [Amount of hardener] The amount of the curing agent may be, relative to 100 parts by weight of the liquid repellent compound, 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, 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.

[0288] [Other ingredients] The repellent may contain other components in addition to the above components. Examples of the other components include polysaccharides, paper strength agents, flocculants, retention aids, coagulants, binder resins, slip prevention agents, sizing agents, paper strength agents, fillers, antistatic agents, preservatives, ultraviolet absorbers, antibacterial agents, deodorants, fragrances, etc. These may be used alone or in combination of two or more. In addition to the above-mentioned components, other components include other water and / or oil repellents, dispersants, texture adjusters, softeners, flame retardants, paint fixing agents, anti-wrinkle agents, drying speed adjusters, crosslinking agents, film-forming agents, compatibilizers, antifreeze agents, viscosity adjusters, UV absorbers, antioxidants, pH adjusters, insect repellents, defoamers, shrink prevention agents, laundry wrinkle prevention agents, shape retention agents, drape retention agents, ironing improvers, whitening agents, whitening agents, fabric softening clay, dye transfer inhibitors such as polyvinylpyrrolidone, polymer dispersants, dirt removers, scum dispersants, fluorescent whitening agents such as 4,4-bis(2-sulfostyryl)biphenyl disodium (Ciba Specialty Chemicals' Chinopearl CBS-X), dye fixatives, and discoloration inhibitors such as 1,4-bis(3-aminopropyl)piperazine. The following can be blended: stain removers, enzymes such as cellulase, amylase, protease, lipase, keratinase, etc. as fiber surface modifiers, foam inhibitors, silk protein powders, their surface modified products or emulsified dispersions (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)), stain prevention agents (e.g., nonionic polymer compounds consisting 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, etc.), etc. These may be used alone or in combination of two or more.

[0289] [Polysaccharide] Examples of polysaccharides include starch, xanthan gum, karaya gum, welan gum, guar gum, pectin, tamarind gum, carrageenan, chitosan, gum arabic, locust bean gum, cellulose, alginic acid, agar, dextran, cellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, chitin nanofiber, cellulose nanofiber, pullulan, etc. The polysaccharide may be a substituted modified polysaccharide (excluding the above-mentioned liquid repellent compounds), in particular a modified polysaccharide into which a hydroxyl group or a cationic group has been introduced.

[0290] [Paper strength agents, flocculants, retention aids or coagulants] Examples of paper strength enhancers, flocculants, retention improvers or coagulants include styrene polymers (styrene / maleic acid polymers, styrene / acrylic acid polymers), urea-formaldehyde polymers, polyethyleneimine, melamine-formaldehyde polymers, polyamidoamine-epichlorohydrin polymers, polyacrylamide polymers, polyamine polymers, polydiallyldimethylammonium chloride, alkylamine-epichlorohydrin condensates, condensates of alkylene dichlorides and polyalkylene polyamines, dicyandiamide-formaldehyde condensates, dimethyldiallylammonium chloride polymers, and olefin / maleic anhydride polymers.

[0291] [Sizing agent] Examples of sizing agents include cellulose-reactive sizing agents, e.g., rosin-based sizing agents such as rosin-based soaps, rosin-based emulsions / dispersions, cellulose-reactive sizing agents, e.g., emulsions / dispersions of acid anhydrides such as alkyl and alkenyl succinic anhydrides (ASA), alkenyl and alkyl ketene dimers (AKD) and polymers, and anionic, cationic and amphoteric polymers of ethylenically unsaturated monomers, e.g., copolymers of styrene and acrylates.

[0292] [Antistatic agent] Examples of the antistatic agent include cationic antistatic agents having cationic functional groups such as quaternary ammonium salts, pyridinium salts, and primary, secondary, and tertiary amino groups; anionic antistatic agents having anionic functional groups such as sulfonates, sulfates, phosphonates, and phosphates; amphoteric antistatic agents such as alkylbetaines and their derivatives, imidazolines and their derivatives, alanines and their derivatives, nonionic antistatic agents such as aminoalcohols and their derivatives, glycerin and its derivatives, and polyethylene glycols and its derivatives. The antistatic agent may be an ion-conductive polymer obtained by polymerizing or copolymerizing monomers having these cationic, anionic, or amphoteric ion-conductive groups. These may be used alone or in combination of two or more.

[0293] [Preservatives] The preservatives are mainly used to enhance the preservative and bactericidal power and maintain the preservative properties during long-term storage. Examples of the preservatives include isothiazolone organic sulfur compounds, benzisothiazolone organic sulfur compounds, benzoic acids, 2-bromo-2-nitro-1,3-propanediol, etc.

[0294] [Ultraviolet absorber] An ultraviolet absorber is a drug that has an ultraviolet protection effect, and is a component that absorbs ultraviolet light and converts it into infrared light, visible light, etc. Examples of ultraviolet absorbers include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole compounds, 4-t-butyl-4'-methoxybenzoylmethane, etc.

[0295] [Antibacterial agents] Antibacterial agents are components that have the effect of suppressing the growth of bacteria on fibers and further suppressing the generation of unpleasant odors resulting from the decomposition products of microorganisms. Examples of antibacterial agents include cationic bactericides such as quaternary ammonium salts, bis-(2-pyridylthio-1-oxide) zinc, polyhexamethylene biguanidine hydrochloride, 8-oxyquinoline, polylysine, etc.

[0296] [Deodorant] Examples of deodorants include cluster dextrin, methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamidopropyldimethylamine oxide, and aminocarboxylic acid metal complexes (zinc complex of trisodium methylglycinediacetate described in WO 2012 / 090580).

[0297] [Amount of other ingredients] The amount or total amount of the other components may be, relative to 100 parts by weight of the liquid repellent compound, 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, 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.

[0298] <Manufacturing method of treated textile or paper products> The method of making a repellent treated product of the present disclosure includes treating a substrate with the repellent agent described above.

[0299] "Treatment" means that the repellent is applied to the substrate by immersion, spraying, coating, etc. The treatment causes the liquid repellent compound, which is the active ingredient of the repellent, to adhere to the inside and / or surface of the substrate. Here, adhesion may be physical adhesion or chemical adhesion, and for example, the liquid repellent compound may be physically or chemically (by reacting with) modified with a hydroxyl group of the substrate (fiber, paper, glass, etc.).

[0300] [Base material] The substrate to be treated with the repellent agent of the present disclosure is not limited, but is preferably a textile product or a paper product, in particular a paper product.

[0301] The repellent agent in the present disclosure provides liquid repellency to a substrate (e.g., a fiber substrate, a paper substrate) and can function as at least one selected from the group consisting of a water repellent agent, an oil repellent agent, an oil-resistant agent, and a water-resistant agent. The substrate treated with the repellent agent in the present disclosure is, for example, oil-resistant paper or water-resistant paper.

[0302] Examples of the substrate for textile products include natural fibers of animal and vegetable origin such as cotton, hemp, wool, silk, etc., synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polypropylene, etc., semi-synthetic fibers such as rayon, acetate, etc., inorganic fibers such as glass fiber, carbon fiber, asbestos fiber, etc., or mixtures of these fibers. Textile products include woven fabrics, knitted fabrics and nonwoven fabrics, clothing forms (e.g., water-repellent clothing, e.g., raincoats), and carpets, but the treatment may be performed on fibers, yarns, and intermediate textile products (e.g., slivers or rovings) before being made into cloth.

[0303] Examples of the substrate for paper products include paper made of bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulp such as groundwood pulp, mechanical pulp or thermomechanical pulp, waste paper pulp such as recycled newsprint, recycled magazine paper, recycled corrugated cardboard or deinked recycled paper, containers made of paper, molded articles made of paper, etc. Specific examples of paper products include food packaging materials, food containers, gypsum board base paper, coated base paper, medium-quality paper, general liners and cores, neutral pure 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 heat-sensitive paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper, molded paper (molded containers), etc., and suitable examples include food packaging materials and food containers.

[0304] Substrates that can be treated with the repellent of the present disclosure are not limited to textiles or paper products, but also include stone, filters (e.g., electrostatic filters), dust masks, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster.

[0305] When the substrate is glass, the glass product to be manufactured may be an optical member. The surface (outermost layer) of the glass substrate may have some layer (or film), such as a hard coat layer or an anti-reflection layer. The anti-reflection layer may be either a single-layer anti-reflection layer or a multi-layer anti-reflection layer. Examples of inorganic substances that can be used for the anti-reflection layer include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, CeO2, MgO, Y2O3, SnO2, MgF2, WO3, etc. These inorganic substances may be used alone or in combination of two or more of them (for example, as a mixture). When a multi-layer anti-reflection layer is used, it is preferable to use SiO2 and / or SiO for the outermost layer. When the product to be manufactured is an optical glass part for a touch panel, a transparent electrode, such as a thin film using indium tin oxide (ITO) or indium zinc oxide, may be provided on a part 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, etc.

[0306] [Processing method] The repellent of the present disclosure can be applied to a substrate as a treatment agent (particularly a surface treatment agent) by a conventionally known method. The treatment method may be a method in which the repellent of the present disclosure is dispersed and diluted in an organic solvent or water as necessary, and attached to the inside and / or surface of the substrate by a known method such as dip coating, spray coating, foam coating, etc., and then dried. After drying, a product is obtained to which the solid components of the repellent are attached. If necessary, it may be applied together with a suitable crosslinking agent and cured. The repellent of the present disclosure may also be used in combination with various additives such as water and / or oil repellents, slip prevention agents, antistatic agents, texture adjusters, softeners, antibacterial agents, flame retardants, paint fixing agents, anti-wrinkle agents, drying speed adjusters, crosslinking agents, film-forming assistants, compatibilizers, antifreeze agents, viscosity adjusters, ultraviolet absorbers, antioxidants, pH adjusters, insect repellents, and defoamers. Examples of various additives may be the same as those described in the "other components" section above. The concentration of the repellent in the treatment agent to be brought into contact with the substrate may be appropriately changed depending on the application, but may be 0.01 to 10% by weight, for example 0.05 to 5% by weight.

[0307] The repellent can be applied to the substrate by any of the methods known for treating substrates with liquids. The substrate may be immersed in the repellent, or the solution may be applied or sprayed onto the substrate. The treated substrate is preferably dried and cured by heating to develop liquid repellency. The heating temperature may be, for example, 100°C to 200°C, 100°C to 170°C, or 100°C to 120°C. In the present disclosure, good performance can be obtained even with low-temperature heating (for example, 100°C to 140°C). In the present disclosure, the heating time may be 5 seconds to 60 minutes, for example, 30 seconds to 3 minutes. When the textile product is paper, the paper may be coated with the repellent, or the solution may be applied or sprayed onto the paper, or the paper may be mixed with the pulp slurry before papermaking and treated. The treatment may be an external addition treatment or an internal addition treatment. Alternatively, the repellent may be applied to the textile product by a cleaning method, for example, by washing application or dry cleaning method.

[0308] [Processing of paper products] The paper substrate may be paper, a paper container, a paper molded body (e.g., a pulp mold), etc. The liquid repellent compound of the present disclosure adheres well to the paper substrate.

[0309] The paper can be produced by a conventional papermaking method, either an internal treatment method in which the repellent is added to the pulp slurry before papermaking, or an external treatment method in which the repellent is applied to the paper after papermaking.

[0310] The size press for external additive treatment can be divided into the following types according to the coating method: One application method is a so-called pond-type two-roll size press, in which a coating liquid (size liquid) is supplied to a nip formed by passing paper between two rubber rolls, a coating liquid pool called a pond is created, and the paper is passed through this coating liquid pool to apply the size liquid to both sides of the paper. Other application methods are a gate roll type in which the size liquid is applied by a surface transfer type, and a rod metering size press. In a pond-type two-roll size press, the size liquid is likely to penetrate into the inside of the paper, and in a surface transfer type, the size liquid component is likely to remain on the surface of the paper. In the surface transfer type, the coating layer is more likely to remain on the surface of the paper than in a pond-type two-roll size press, and the coating layer formed on the surface is larger than in a pond-type two-roll size press. In the present disclosure, performance can be imparted to the paper even when the former pond-type two-roll size press is used. The paper thus treated can exhibit excellent oil resistance, water resistance, etc. by optionally accompanying a heat treatment that can take a temperature range of up to 300°C, for example up to 200°C, particularly 80°C to 180°C, depending on the properties of the paper, after simple drying at room temperature or high temperature.

[0311] The internal addition treatment method may mean a treatment method of adding a repellent to a pulp slurry before papermaking. The internal addition treatment method may include, but is not limited to, one or more of the steps of adding a repellent to a pulp slurry and stirring and mixing it, suction-dehydrating the pulp composition prepared in the step through a mesh body of a predetermined shape to deposit the pulp composition to form a pulp mold intermediate, and molding and drying the pulp mold intermediate with a heated mold to obtain paper, a paper container, or a paper molded article. The treated paper may be heat-treated, depending on the properties of the paper, after simple drying at room temperature or at a high temperature. The temperature of the heat treatment may be 150°C or higher, 180°C or higher, or 210°C or higher, and may be 300°C or lower, 250°C or lower, or 200°C or lower, and may be particularly 80°C to 180°C. By performing heat treatment in such a temperature range, excellent oil resistance and water resistance can be exhibited.

[0312] The present disclosure can be used in gypsum board base paper, coated base paper, medium quality paper, general liners and cores, neutral pure white roll paper, neutral liners, rust-proof liners and metal interleaving paper, kraft paper, etc. It can also be used in neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper, and neutral information paper.

[0313] Pulp raw materials include bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, groundwood pulp, mechanical pulp, or thermomechanical pulp. Any of bleached or unbleached high-yield pulp, recycled newspaper, magazine, corrugated cardboard, deinked recycled paper, etc. may be used. Mixtures of the above pulp raw materials with synthetic fibers such as asbestos, polyamide, polyimide, polyester, polyolefin, polyvinyl alcohol, etc. may also be used.

[0314] The water resistance of paper can be improved by adding a sizing agent. Examples of the sizing agent include cationic sizing agents, anionic sizing agents, and rosin-based sizing agents (e.g., acidic rosin-based sizing agents, neutral rosin-based sizing agents). The amount of the sizing agent may be 0.01 to 5% by weight based on the pulp.

[0315] If necessary, the paper may contain additives used in the manufacture of paper, such as paper strength enhancers such as starch, modified starch, carboxymethyl cellulose, and polyamide polyamine-epichlorohydrin resin, flocculants, fixing agents, retention improvers, dyes, fluorescent dyes, slime control agents, and defoamers, to the extent that they are commonly used. Starch and modified starch are preferably used. If necessary, repellents can be applied to the paper using starch, polyvinyl alcohol, dyes, coating colors, anti-slip agents, and the like, by a size press, gate roll coater, bill blade coater, calendar, or the like.

[0316] In the case of external addition, the amount of the liquid repellent compound contained in the coating layer is 0.01 to 2.0 g / m 2 , especially 0.1 to 1.0 g / m 2 The coating layer is preferably formed from a repellent and starch and / or modified starch. The solid content of the paper repellent in the coating layer is preferably 2 g / m 2 It is preferable that: In the case of internal addition, it is preferable to mix the repellent with the pulp so that the amount of the repellent is 0.01 to 50 parts by weight or 0.01 to 30 parts by weight, for example 0.01 to 10 parts by weight, and particularly 0.2 to 5.0 parts by weight, per 100 parts by weight of the pulp forming the paper.

[0317] In the case of external addition, oil resistance can also be imparted to paper by using a so-called pond-type two-roll size press process in which the treatment solution is pooled between rolls and the base paper is passed through the treatment solution between the rolls at any roll speed and nip pressure.

[0318] In the external addition treatment, the paper substrate may contain additives such as sizing agents, paper strength agents, flocculants, retention agents or coagulants. The additives may be nonionic, cationic, anionic or amphoteric. The ionic charge density of the additives may be -10000 to 10000 μeq / g, preferably -4000 to 8000 μeq / g, more preferably -1000 to 7000 μeq / g. Additives such as sizing agents, paper strength agents, flocculants, retention agents or coagulants (solids or active ingredients) can generally be used in an amount of 0.1 to 10% by weight (e.g., 0.2 to 5.0% by weight) based on the pulp. In the case of a paper substrate containing a cationic additive (e.g., sizing agents, paper strength agents, flocculants, retention agents or coagulants), the repellent is preferably anionic.

[0319] In the internal addition treatment, it is preferable to make a pulp slurry having a pulp concentration of 0.5 to 5.0% by weight (for example, 2.5 to 4.0% by weight). Additives (for example, sizing agents, paper strength agents, flocculants, retention agents, coagulants, etc.) and liquid repellent compounds can be added to the pulp slurry. Examples of additives (e.g., sizing agents, paper strength agents, flocculants, retention agents, or coagulants) include alkylketene dimers, alkenyl succinic anhydrides, styrene polymers (styrene / maleic acid polymers, styrene / acrylic acid polymers), urea-formaldehyde polymers, polyethyleneimine, melamine-formaldehyde polymers, polyamidoamine-epichlorohydrin polymers, polyacrylamide polymers, polyamine polymers, polydiallyldimethylammonium chloride, alkylamine-epichlorohydrin condensates, condensates of alkylene dichlorides and polyalkylenepolyamines, dicyandiamide-formaldehyde condensates, dimethyldiallylammonium chloride polymers, and olefin / maleic anhydride polymers.

[0320] [Pretreatment of textile products] The textile product may be pretreated before being treated with the repellent of the present disclosure. Pretreatment of the textile product may impart excellent fastness to the textile product after treatment with the repellent.

[0321] Examples of pretreatments of textile products include cationization treatment by reaction with a reactive quaternary ammonium salt, anionization treatment such as sulfonation, carboxylation, and phosphation, and acetylation treatment, benzoylation treatment, carboxymethylation treatment, grafting treatment, tannic acid treatment, and polymer coating treatment after anionization treatment.

[0322] The method for pretreating a textile product is not limited, and the textile product can be pretreated by a conventionally known method. The pretreatment liquid may be dispersed and diluted in an organic solvent or water as necessary, and applied to the inside and / or surface of the textile product by a known method such as dip coating, spray coating, foam coating, etc., and then dried. The pH and temperature of the pretreatment liquid may be adjusted depending on the desired degree of treatment. As an example of the method for pretreating a textile product, a method for pretreating a textile product with the above-mentioned treatment agent will be described in detail.

[0323] The pretreatment method for textile products is to add -SO3M to the fibers. 1 (In the formula, M 1 represents a monovalent cation), -COOM 2 (In the formula, M 2 represents a monovalent cation), and -OP(O)(OX 1 )(OX 2 )(wherein, X 1 and X 2 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms) (hereinafter, also referred to as "specific functional groups").

[0324] M 1 Examples of M include H, K, Na, and ammonium ion which may have a substituent. 2 Examples of X include H, K, Na, and ammonium ion which may have a substituent. 1 Or X 2 When is an alkyl group, it is preferably an alkyl group having 1 to 22 carbon atoms, and more preferably an alkyl group having 4 to 12 carbon atoms.

[0325] The fibers containing the specific functional groups (hereinafter, sometimes referred to as "functional group-containing fibers") can be prepared, for example, by the following method. (i) A compound having the specific functional group is attached to a fiber material. The attachment of the compound may be in a state where a part of the compound is chemically bonded to a part of the fiber to the extent that a sufficient amount of the specific functional group remains. (ii) A fiber is prepared in which the specific functional group is directly introduced into the material constituting the fiber.

[0326] In the case of (i), for example, a functional group-containing fiber can be obtained by a functional group introduction step in which a fiber material is treated with a pretreatment liquid containing one or more compounds having the specific functional group.

[0327] The material of the fiber material is not particularly limited, and examples thereof include natural fibers such as cotton, hemp, silk, wool, etc., semi-synthetic fibers such as rayon, acetate, etc., synthetic fibers such as polyamide (nylon, etc.), polyester, polyurethane, polypropylene, etc., and composite fibers, blended fibers, etc. The form of the fiber material may be any of fibers (tow, sliver, etc.), yarn, knitted fabric (including interwoven fabric), woven fabric (including interwoven fabric), nonwoven fabric, etc.

[0328] In this embodiment, from the viewpoint of improving the water repellency of the obtained textile product, it is preferable to use textile materials containing polyamide and polyester as raw materials, and in particular, it is preferable to use nylons such as nylon 6 and nylon 6,6, polyesters such as polyethylene terephthalate (PET), polytrimethyl terephthalate, and polylactic acid, and mixed fibers containing these.

[0329] Above -SO3M 1 As the compound having the formula (I), a phenol-based polymer can be used. As such a phenol-based polymer, for example, one containing at least one compound represented by the following general formula can be mentioned.

[0330] TIFF2025023980000010.tif4770 [where, X 2 Ha-SO3M 3 (In the formula, M 3 represents a monovalent cation) or a group represented by the following general formula, and n is an integer of 20 to 3000.

[0331] TIFF2025023980000011.tif2758 [In the formula, M 4 represents a monovalent cation.

[0332] The above M 3 Examples of the cation include H, K, Na, and ammonium ion which may have a substituent.

[0333] The above M 4 Examples of the cation include H, K, Na, and ammonium ion which may have a substituent.

[0334] The compound represented by the above general formula may be, for example, a formalin condensate of phenolsulfonic acid or a formalin condensate of sulfonated bisphenol S.

[0335] Above - COOM 2 Examples of compounds having the formula include polycarboxylic acid polymers.

[0336] As the polycarboxylic acid polymer, for example, a polymer synthesized by a conventionally known radical polymerization method using acrylic acid, methacrylic acid, maleic acid, or the like as a monomer, or a commercially available product can be used.

[0337] Examples of the method for producing a polycarboxylic acid polymer include a method in which a radical polymerization initiator is added to an aqueous solution of the above-mentioned monomer and / or its salt, and the solution is heated and reacted at 30 to 150° C. for 2 to 5 hours. At this time, an alcohol such as methanol, ethanol, isopropyl alcohol, or an aqueous solvent such as acetone may be added to the aqueous solution of the above-mentioned monomer and / or its salt. Examples of the radical polymerization initiator include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, redox-based polymerization initiators such as combinations of persulfates and sodium bisulfite, hydrogen peroxide, and water-soluble azo-based polymerization initiators. These radical polymerization initiators may be used alone or in combination of two or more. Furthermore, during radical polymerization, a chain transfer agent (e.g., octyl thioglycolate) may be added for the purpose of adjusting the degree of polymerization.

[0338] In addition to the above monomers, copolymerizable monomers can be used in the radical polymerization. Examples of the copolymerizable monomers include vinyl monomers such as ethylene, vinyl chloride, and vinyl acetate, acrylamide, acrylates, and methacrylates. The acrylates and methacrylates are preferably those having a hydrocarbon group having 1 to 3 carbon atoms which may have a substituent such as a hydroxyl group. Examples of such acrylates or methacrylates include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, propyl acrylate, and propyl methacrylate. These copolymerizable monomers may be used alone or in combination of two or more.

[0339] The carboxyl group in the polycarboxylic acid polymer may be free or may be neutralized with an alkali metal, an amine compound, etc. Examples of the alkali metal include sodium, potassium, and lithium, and examples of the amine compound include ammonia, monoethanolamine, diethanolamine, and triethanolamine.

[0340] The weight average molecular weight of the polycarboxylic acid polymer is preferably from 1,000 to 20,000, and more preferably from 3,000 to 15,000, from the viewpoint of improving the water repellency of the resulting textile product.

[0341] As the polycarboxylic acid polymer, commercially available products such as "Neocrystal 770" (product name, manufactured by Nicca Chemical Co., Ltd.) and "Ceropol PC-300" (product name, manufactured by Sanyo Chemical Industries, Ltd.) can be used.

[0342] Above -OP(O)(OX 1 )(OX 2 ) is exemplified by a phosphate ester compound represented by the following general formula: TIFF2025023980000012.tif3236[where, X 1 Or X 2 is the same as above, and X 3 represents an alkyl group having 1 to 22 carbon atoms.

[0343] As the phosphate ester compound, phosphate monoesters, diesters and triesters, in which the alkyl ester moiety is an alkyl group having 1 to 22 carbon atoms, and mixtures thereof can be used.

[0344] From the viewpoint of improving the water repellency of the resulting textile product, it is preferable to use lauryl phosphate and decyl phosphate.

[0345] As the phosphate ester compound, for example, a commercially available product such as "Phosphanol ML-200" (product name, manufactured by Toho Chemical Industry Co., Ltd.) can be used.

[0346] The pretreatment liquid containing one or more compounds having the specific functional group may be, for example, an aqueous solution of the above-mentioned compounds. The pretreatment liquid may also contain an acid, an alkali, a surfactant, a chelating agent, etc.

[0347] Examples of the method for treating the textile material with the pretreatment liquid include padding, immersion, spraying, and coating. Examples of padding include a method using a padding device described on pages 396-397 of Textile Dyeing and Processing Dictionary (published by Nikkan Kogyo Shimbun, 1963) and pages 256-260 of Color Dyeing Chemistry III (published by Jikkyo Publishing Co., Ltd., 1975). Examples of coating include a method using a coating machine described on pages 473-477 of Dyeing and Finishing Equipment Directory (published by Sen-sha, 1981). Examples of immersion include a method using a batch-type dyeing machine described on pages 196-247 of Dyeing and Finishing Equipment Directory (published by Sen-sha, 1981), and a liquid flow dyeing machine, air flow dyeing machine, drum dyeing machine, winch dyeing machine, washer dyeing machine, cheese dyeing machine, etc. can be used. Examples of the spray treatment include an air spray in which the treatment liquid is sprayed in the form of a mist using compressed air, and a method using an air spray of a liquid pressure atomization type. The treatment conditions, such as the concentration of the treatment liquid and the heat treatment after application, can be appropriately adjusted in consideration of various conditions such as the purpose and performance. In addition, when the pretreatment liquid contains water, it is preferable to dry the pretreatment liquid after it is applied to the fiber material in order to remove the water. There is no particular limit to the drying method, and either a dry heat method or a wet heat method may be used. There is also no particular limit to the drying temperature, and for example, drying may be performed at room temperature to 200°C for 10 seconds to several days. If necessary, heat treatment may be performed at a temperature of 100 to 180°C for about 10 seconds to 5 minutes after drying.

[0348] When the textile material is to be dyed, the treatment with the pretreatment liquid may be carried out before dyeing or in the same bath as the dyeing. However, when reduction soaping is carried out, there is a risk that the compound having the specific functional group (e.g., a phenolic polymer compound, etc.) adsorbed during the process may fall off, so it is preferable to carry out the treatment after reduction soaping after dyeing.

[0349] The treatment temperature in the immersion treatment can be 60 to 130° C. The treatment time can be 5 to 60 minutes.

[0350] In the functional group introduction step using a pretreatment liquid, the amount of the compound having the specific functional group attached is preferably 1.0 to 7.0 parts by weight per 100 parts by weight of the textile material. Within this range, durable water repellency and texture can be simultaneously achieved at high levels.

[0351] The pretreatment liquid is preferably adjusted to a pH of 3 to 5. The pH can be adjusted using a pH adjuster such as acetic acid or malic acid.

[0352] In the pretreatment solution, a salt may be used in combination in order to effectively adsorb the compound having the specific functional group to the fiber material by the salting-out effect. Examples of the salt that can be used include sodium chloride. Examples of suitable salts include sodium carbonate, ammonium sulfate, and sodium sulfate.

[0353] In the functional group introduction step using the pretreatment liquid, it is preferable to remove the compound having the specific functional group that has been treated in excess. An example of a removal method is washing with water. By removing the compound sufficiently, it is possible to prevent the development of water repellency in the subsequent water repellent treatment from being hindered, and in addition, the texture of the obtained textile product is improved. In addition, it is preferable to thoroughly dry the obtained functional group-containing fiber before contacting it with the above-mentioned treatment agent.

[0354] (ii) An example of a fiber in which the specific functional group is directly introduced into the material constituting the fiber is cationic dyeable polyester (CD-PET).

[0355] From the viewpoint of improving the water repellency of the resulting textile product, the functional group-containing fiber preferably has a surface zeta potential of −100 to −0.1 mV, more preferably −50 to −1 mV. The zeta potential of the fiber surface can be measured, for example, by a zeta potential / particle size measuring system ELSZ-1000ZS (manufactured by Otsuka Electronics Co., Ltd.).

[0356] Although the embodiments have been described above, it will be understood that various changes in form and details are possible without departing from the spirit and scope of the claims. EXAMPLES

[0357] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to these examples.

[0358] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to these examples.

[0359] <Test Method> The test procedure is as follows.

[0360] [Volume ratio of particles 1μm or larger] The abundance ratio of particles 1 μm or larger was calculated from the volume-based frequency distribution (volume distribution) obtained by measuring the water-dispersed repellent using a laser diffraction / scattering device, and this value was taken as the volume abundance ratio of particles 1 μm or larger.

[0361] [Median diameter D50] The repellency of the water-dispersed agent was determined by measurement using a laser diffraction / scattering device.

[0362] [HD contact angle] A solution (or dispersion) of the liquid-repellent compound with a solid content concentration of 1.0% was spin-coated on a silicon wafer at 2500 rpm for 25 seconds to obtain a spin-coated film. This was heated at 140°C for 1 minute to produce a silicon wafer treated with the liquid-repellent compound. Chloroform was used as the solvent or dispersion medium. 2 μL of HD (hexadecane) was dropped onto the silicon wafer treated with the liquid-repellent compound, and the contact angle 1 second after the drop landed was taken as the HD contact angle of the liquid-repellent compound.

[0363] [Water contact angle] A solution (or dispersion) of the liquid-repellent compound with a solid content concentration of 1.0% was spin-coated on a silicon wafer at 2500 rpm for 25 seconds to obtain a spin-coated film. This was heated at 140°C for 1 minute to produce a silicon wafer treated with the liquid-repellent compound. Chloroform was used as the solvent or dispersion medium. 2 μL of water was dropped onto the silicon wafer treated with the liquid-repellent compound, and the contact angle 1 second after the drop landed was taken as the water contact angle of the liquid-repellent compound.

[0364] [Making pulp molds] Pulp mold was formed using an automatic molding machine. A mesh-like body was placed on a metal pulp mold mold with many suction holes at the bottom, and a metal tank was placed at the top, with a mixture of pulp slurry and water-dispersed repellent being placed in the upper metal tank. The pulp-containing aqueous composition was sucked and dehydrated through the pulp mold mold and mesh-like body by a vacuum pump from the side opposite to the side where the mesh-like body was placed in the pulp mold mold, and the solid content (pulp, etc.) contained in the pulp-containing aqueous composition was deposited on the mesh-like body to obtain a pulp mold intermediate. Next, the obtained pulp mold intermediate was dried under a pressure of 0.05 to 5 MPa from above and below in a male-female metal mold heated to 60 to 250°C. This produced a pulp molded product molded into the shape of a container.

[0365] [65℃ oil resistance test] The pulp mold was pretreated by storing it under conditions of 23°C and 50% humidity for 12 hours. 100 ml of corn oil at 65°C was poured into the pulp mold and left at room temperature for 45 minutes, after which the corn oil was removed from the pulp mold and the degree of soaking into the pulp mold was evaluated. The following evaluation values ​​were set according to the degree of soaking. 5: No stains on the inside 4: Stain on the inside. No stain on the back. 3: Stain on the inside. Slight seepage on the back. 2: Stain on the inside. Less than 50% of the area has seeped through to the back. 1: Stain on the inside. Stain on the back is 50% or more but less than 100% of the area. 0: Seeping through to the entire back side.

[0366] [Measurement of ionic charge density] The anion demand of a 0.1g / L sample solution is measured using a particle charge meter (BTG MUTEK PCD-04) with a 1 / 1000 N solution of potassium polyvinyl sulfonate, and the ionic charge density (cationic charge density) is calculated using the following formula (1). Alternatively, the cation demand is measured in the same manner using a solution of polydiallyldimethylammonium chloride 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 solution concentration (g / L)

[0367] [Preparation of treated paper] A pulp slurry was prepared with a weight ratio of 60% LBKP (hardwood bleached kraft pulp) and 40% NBKP (softwood bleached kraft pulp) as wood pulp, and with a pulp freeness of 400 ml (Canadian Standard Freeness). A wet strength agent and a sizing agent were added to the pulp slurry, and the paper was spun on a fourdrinier paper machine to a paper density of 0.58 g / cm. 3 Grammage: 45g / m 2 The paper was used as the base paper for external treatment (size press treatment). The oil resistance (KIT value) of this base paper was 0, and the water resistance (Cobb value) was 52 g / m 2 It was.

[0368] A treatment solution in which the compound was dissolved in chloroform at a ratio of 14.9 mg / mL was applied to this base paper using a Baker-type applicator with a gap set to 0 mil and dried three times, and then dried at 140°C for one minute to produce treated paper.

[0369] [Dispersion stability test] The water-dispersed repellent was left to stand at 25°C for 100 hours, and the state of the dispersion was checked. If the supernatant liquid became transparent and the dispersoid and the aqueous medium were separated, it was rated as "△: poor", and if the dispersoid and the aqueous medium were not separated, it was rated as "〇: good". EXAMPLES

[0370] 2g of decaglycerol dodecabehenyl ester (polyol modified, polymerization degree 10, hydroxyl group substitution rate: 12 / 12*100 [100%], biobased degree: 100%) as a liquid repellent compound, 0.2g of benzalkonium chloride, and 17.8g of water were mixed to obtain a precursor A of a water-dispersed repellent. This precursor A of a water-dispersed repellent was heated to 80°C, and then cooled while stirring with a magnetic stirrer to obtain a precursor B of a water-dispersed repellent. The precursor B of a water-dispersed repellent was treated three times under a condition of 245MPa in a high-pressure wet microparticulation device to obtain a water-dispersed repellent. The volumetric ratio of particles of 1μm or more in the obtained water-dispersed repellent was 21%, and the median diameter D50 was 0.68μm. The ionic charge density was +127 μeq / g. When the water-dispersible repellent was subjected to a dispersion stability test, the dispersibility was good. The water-dispersed repellent was added to a pulp slurry with a concentration of 0.5 wt% so that the ratio of the repellent to the pulp was 4 wt% in terms of solid content, to prepare a pulp-containing water-dispersed repellent. The pulp-containing water-dispersed repellent was placed in an automatic molding machine to produce a pulp mold. When the pulp mold was subjected to an oil resistance test at 65°C, it received a score of 4. The results are shown in Table 1. EXAMPLES

[0371] 2 g of decaglycerol dodecabehenyl ester (polyol modified, polymerization degree 10, hydroxyl group substitution rate: 12 / 12*100 [100%], biobased degree: 100%) as a liquid repellent compound, 0.1 g of benzalkonium chloride, and 17.9 g of water were mixed to obtain a precursor A of a water-dispersed repellent. This precursor A of a water-dispersed repellent was heated to 80°C, and then cooled while stirring with a magnetic stirrer to obtain a precursor B of a water-dispersed repellent. The precursor B of a water-dispersed repellent was treated three times under a condition of 245 MPa in a high-pressure wet microparticulation device to obtain a water-dispersed repellent. The volumetric ratio of particles of 1 μm or more in the obtained water-dispersed repellent was 25%, and the median diameter D50 was 0.52 μm. The ionic charge density was +41 μeq / g. When the water-dispersed repellent was subjected to a dispersion stability test, the dispersibility was good. The water-dispersed repellent was added to a pulp slurry with a concentration of 0.5 wt% so that the ratio of the repellent to the pulp was 4 wt% in terms of solid content, to prepare a pulp-containing water-dispersed repellent. The pulp-containing water-dispersed repellent was placed in an automatic molding machine to produce a pulp mold. When the pulp mold was subjected to an oil resistance test at 65°C, it received a score of 4. The results are shown in Table 1. EXAMPLES

[0372] 2 g of decaglycerol decabehenyl ester (polyol modified, polymerization degree 10, hydroxyl group substitution rate: 7 / 12*100 [58%], biobased degree: 100%) as a liquid repellent compound, 0.2 g of benzalkonium chloride, and 17.8 g of water were mixed to obtain a precursor A of a water-dispersed repellent. This precursor A of a water-dispersed repellent was heated to 80°C, and then cooled while stirring with a magnetic stirrer to obtain a precursor B of a water-dispersed repellent. The precursor B of a water-dispersed repellent was treated three times under a condition of 245 MPa in a high-pressure wet microparticulation device to obtain a water-dispersed repellent. The volumetric ratio of particles of 1 μm or more in the obtained water-dispersed repellent was 18%, and the median diameter D50 was 0.78 μm. The ionic charge density was +118 μeq / g. When the water-dispersed repellent was subjected to a dispersion stability test, the dispersibility was good. The water-dispersed repellent was added to a pulp slurry with a concentration of 0.5 wt% so that the ratio of the repellent to the pulp was 4 wt% in terms of solid content, to prepare a pulp-containing water-dispersed repellent. The pulp-containing water-dispersed repellent was placed in an automatic molding machine to produce a pulp mold. When the pulp mold was subjected to an oil resistance test at 65°C, it received a score of 4. The results are shown in Table 1. EXAMPLES

[0373] A biodegradability test was conducted on decaglycerol dodecabehenyl ester (degree of polymerization 10, hydroxyl group substitution rate: 12 / 12*100 [100%], biobased content: 100%) according to JIS K 6953-1:2011. After 30 days of testing, the biodegradability was 36%, after 60 days, the biodegradability was 62%, and after 180 days, the biodegradability was 94%. EXAMPLES

[0374] Based on JIS K 6953-1:2011, a biodegradability test was conducted on decaglycerol decabehenyl ester (degree of polymerization: 10, hydroxyl group substitution rate: 7 / 12*100 [58%], biobased content: 100%). The biodegradability was 40% after 30 days of the test period, and 60% after 60 days of the test period. Comparative Example 1

[0375] As a liquid repellent compound, 2g of decaglycerol dodecabehenyl ester (polyol modified, polymerization degree 10, hydroxyl group substitution rate: 12 / 12*100 [100%], biobased degree: 100%), 0.2g of polyethylene oxide alkyl ether (alkyl carbon number 6 to 16 HLB: 7), and 17.8g of water were mixed to obtain a precursor A of a water-dispersed repellent. This precursor A of a water-dispersed repellent was heated to 80°C, and then cooled while stirring with a magnetic stirrer to obtain a precursor B of a water-dispersed repellent. The precursor B of a water-dispersed repellent was treated three times under a condition of 245 MPa in a high-pressure wet microparticulation device to obtain a water-dispersed repellent. The volumetric ratio of particles of 1 μm or more in the obtained water-dispersed repellent was 24%, and the median diameter D50 was 0.81 μm. The ionic charge density was -107 μeq / g. When the water-dispersible repellent was subjected to a dispersion stability test, the dispersibility was good. The water-dispersed repellent was added to a pulp slurry with a concentration of 0.5 wt% so that the ratio of the repellent to the pulp was 4 wt% in terms of solid content, to prepare a pulp-containing water-dispersed repellent. The pulp-containing water-dispersed repellent was placed in an automatic molding machine to produce a pulp mold. The pulp mold was subjected to an oil resistance test at 65°C and scored 2 points. The results are shown in Table 1. Comparative Example 2

[0376] As a liquid repellent compound, 2 g of decaglycerol dodecabehenyl ester (polyol modified, polymerization degree 10, hydroxyl group substitution rate: 12 / 12*100 [100%], biobased degree: 100%), 0.2 g of polyethylene oxide alkyl ether (alkyl carbon number 6 to 16 HLB: 7), and 17.8 g of water were mixed to obtain a precursor A of a water-dispersed repellent. This precursor A of a water-dispersed repellent was heated to 80°C, and then cooled while stirring with a magnetic stirrer to obtain a water-dispersed repellent. The volumetric abundance ratio of particles of 1 μm or more in the obtained water-dispersed repellent was 82%, and the median diameter D50 was 57.1 μm. The ionic charge density was -80.9 μeq / g. When the water-dispersed repellent was subjected to a dispersion stability test, the dispersibility was poor. The water-dispersed repellent was added to a pulp slurry with a concentration of 0.5 wt% so that the ratio of the repellent to the pulp was 4 wt% in terms of solid content, to prepare a pulp-containing water-dispersed repellent. The pulp-containing water-dispersed repellent was placed in an automatic molding machine to produce a pulp mold. When the pulp mold was subjected to an oil resistance test at 65°C, it received a score of 1. The results are shown in Table 1.

[0377] [Table 1] JPEG2025023980000013.jpg108164

[0378] By setting the volumetric ratio of particles of 1 μm or more in the water-dispersible repellent to 30% or less and using a cationic dispersant, it is possible to achieve both dispersion stability and oil resistance at 65°C.

Claims

1. A liquid repellent compound which is at least one selected from the group consisting of polyol-modified compounds and amine-modified compounds, and Cationic Dispersants A water-dispersible repellent comprising:

2. 2. The repellent according to claim 1, wherein the volumetric ratio of particles having a size of 1 μm or more is 30% or less as measured by a laser diffraction scattering method.

3. The repellent according to claim 1 , having an ionic charge density of 1 μeq / g or more and 1000 μeq / g or less.

4. The repellent of claim 1 comprising a nonionic dispersant.

5. The polyol modified product is a compound obtained by modifying a polyol with a monovalent hydrocarbon group having from 1 to 40 carbon atoms, which may have a substituent, or a monovalent polysiloxane group; The repellent according to claim 1, wherein the amine-modified product is a compound obtained by modifying an amine with a monovalent hydrocarbon group having 1 to 40 carbon atoms, which may have a substituent, or a monovalent polysiloxane group.

6. The polyol modification product is a compound obtained by modifying a polyol with an alkyl group having 6 to 40 carbon atoms; The repellent according to claim 1 , wherein the amine-modified compound is a compound obtained by modifying an amine with an alkyl group having 6 to 40 carbon atoms.

7. The polyol modification may be achieved by modifying one or more hydroxy groups of the polyol with the formula: -Y-Z ｎ [In the formula, Y is Y １ and Y ２ is a 1+n valent group consisting of one or more selected from the group consisting of Y １ is a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O) ２ -, -NR'-, -C(OR')R'-, and -C(OR')(-) ２ , -N(-) ２ (wherein R' is independently at each occurrence a hydrogen atom or an organic group having 1 to 30 carbon atoms); Y ２ is a group consisting of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent aromatic hydrocarbon rings, and optionally substituted di- to tetravalent heterocycles, Z is a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group which may have a substituent, n is an integer of 1 to 3. is a compound substituted with a group represented by The amine-modified an amine backbone, and The following formula: -X-Z ｎ [X is X １ and X ２ is a 1+n valent group consisting of one or more selected from the group consisting of X １ is a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O) ２ -, -NR'-, -C(OR')R'-, and -C(OR')(-) ２ , -N(-) ２ (wherein R' is independently at each occurrence a hydrogen atom or an organic group having 1 to 30 carbon atoms); X ２ is a group consisting of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent aromatic hydrocarbon rings, and optionally substituted di- to tetravalent heterocycles, Z is a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group which may have a substituent, n is an integer of 1 to 3. has one or more groups represented by At least one -X-Z ｎ The repellent according to claim 1 , which is a compound in which:

8. Y of the modified polyol is -O-Y １１ - or -O-Y １１ -Y ２１ -Y １２ - wherein each symbol represents independently at each occurrence: Y １１ is a direct bond, -C(=O)-, -C(=O)-NR'-, or -C(=S)-NR'-; Y ２１ is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, Y １２ が-O-、-O-C(=O)-、-O-C(=O)-O-、-C(=O)-NR-、-O-C(=O)-OR-、-O-C(=O)-O-、--O--- O)-、-NR'-C(=O)-O-、-NR’-C(=O)-NR’-、-C(=O)-、-C(=O)-O-、-C(=O)-[O---- ２ -、-S ２ NR'-、-C(OR')(-) ２ かる。] and The amine-modified The following formula: N(-X-Z n ) p (-H) q -L 1 -[N(-X-Z n ) r (-H) s -L 1 -] t -N(-X-Z n ) p (-H) q [In the formula, X and Z are independently in each occurrence as defined above; 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 oxygen atoms and / or sulfur atoms; n is independently in each occurrence an integer from 1 to 3, p, in each occurrence, is an integer between 0 and 2, inclusive; q is independently in each occurrence an integer from 0 to 2, p+q is each N(-XZ n ) p (-H) q In the above, r is independently in each occurrence 0 or 1; s is independently in each occurrence 0 or 1; r+s is each N(-XZ n ) r (-H) s In the sum of all p's and all r's is greater than or equal to 1; t is an integer of 0 to 10. or The following formula: N(-X-Z n ) p (-H) q -L ２ (-X-Z n ) u [In the formula, X and Z are independently in each occurrence as defined above; L ２ represents an aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms and a valence of 1+u, which may be interrupted by an oxygen atom and / or a sulfur atom, n is independently in each occurrence an integer from 1 to 3, optionally interrupted by oxygen and / or sulfur atoms; p is an integer of 0 to 2, q is an integer of 0 to 2, p+q is 2, u is an integer of 1 to 3, The sum of p and u is 1 or greater. The repellent according to claim 7, which is a compound represented by the formula:

9. the polyol is at least one selected from the group consisting of monosaccharides, oligosaccharides, polysaccharides, sugar alcohols, hydroxy acids, amino acids, vitamins, flavonols, hydroxy hydrocarbons, and hydroxy group-containing compound polymers; The repellent of claim 1 , wherein the amine is an organic amine.

10. The polyol is Glucose, fructose, galactose, xylose; Sucrose, cycloamylose, cyclodextrin, maltose, trehalose, lactose, sucralose; Sorbitol, maltitol, erythritol, isomalt, lactitol, mannitol, xylitol, sorbitan, lactitol; Starch, cellulose, curdlan, pullulan, alginic acid, carrageenan, guar gum, chitin, chitosan, locust bean gum, kappa carrageenan, iota carrageenan, isomaltodextrin, gellan gum, tamarind seed gum; Ascorbic acid, kojic acid, quinic acid, chlorogenic acid, gluconic acid; Glucosamine; Inositol; Catechins, quercetin, anthocyanins; Glycerin, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, trimethylolpropane, trimethylolethane; At least one selected from the group consisting of polyglycerin, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymers, hydroxypropyl (meth)acrylate polymers, and hydroxybutyl (meth)acrylate polymers; The repellent according to claim 1 , wherein the amine is at least one selected from the group consisting of alkylenediamines, alkylenetriamines, alkylenetetramines, and aromatic amines.

11. The repellent of claim 1 , wherein the cationic dispersant is a quaternary ammonium salt.

12. The repellent according to claim 1 , wherein the polyol-modified or amine-modified compound has a bio-based content of 20% or more.

13. The repellent of claim 1 , wherein the amine-modified moiety is a polyamide.

14. the liquid repellent compound is the modified polyol, The polyol modification product is a product in which a hydroxy group possessed by a polyglycerol having a polymerization degree of 5 to 15 is converted into a hydroxy group represented by the following formula: -OC(=O)-Z [In the formula, Z is an alkyl group having 14 to 24 carbon atoms. is a compound substituted with a group represented by The repellent according to claim 1 , wherein the hydroxyl group substitution rate in the modified polyol is 50% or more.

15. The repellent according to claim 1, which is for use in textile products or paper products.

16. A product treated with the repellent according to any one of claims 1 to 15.

17. 17. The product of claim 16 which is a textile or paper product.

18. 17. The product of claim 16 which is a greaseproof or waterproof paper.

19. 17. The article of claim 16 which is a food packaging or food container.

20. A method for producing a treated product comprising treating a substrate with a repellent agent according to any one of claims 1 to 15.

21. The method according to claim 20, wherein the treatment is an internal addition treatment.

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