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] This disclosure relates to repellents and products treated with repellents. [Background technology]

[0002] In recent years, development has been progressing on non-fluorine-based repellents that can impart liquid repellency (water repellency, oil repellency, oil resistance, and / or water resistance) to various substrates. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2021-155492 [Overview of the project] [Problems that the invention aims to solve]

[0004] Patent Document 1 does not describe oil resistance. Patent Document 1 does not describe the use of cationic dispersants. Furthermore, Patent Document 1 does not examine the effect of particle size in the repellent on oil resistance.

[0005] The object of this disclosure is to provide a novel oil-repellent agent that can impart oil resistance to a substrate (e.g., fibers, paper). [Means for solving the problem]

[0006] This 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 dispersant A water-dispersible repellent containing [a specific component]. [Section 2] The repellent according to item 1, wherein the volume abundance ratio of particles larger than 1 μm, as measured by laser diffraction scattering, is 30% or less. [Section 3] A repellent agent according to item 1 or 2, wherein the ion charge density is 1 μeq / g or more and 1000 μeq / g or less. [Section 4] A repellent agent according to any one of items 1 to 3, comprising a nonionic dispersant. [Section 5] The polyol-modified compound is a compound obtained by modifying a polyol with a monovalent hydrocarbon group having 1 to 40 carbon atoms, which may have substituents, or a monovalent polysiloxane group; The repellent according to any one of claims 1 to 4, wherein the amine-modified compound is a compound obtained by modifying an amine with a monovalent hydrocarbon group having 1 to 40 carbon atoms, which may have substituents, or a monovalent polysiloxane group. [Section 6] The polyol-modified compound is a compound obtained by modifying a polyol with an alkyl group having 6 to 40 carbon atoms; The repellent according to any one of claims 1 to 5, wherein the amine-modified compound is a compound obtained by modifying an amine with an alkyl group having 6 to 40 carbon atoms. [Section 7] The aforementioned polyol modified product has one or more hydroxyl groups of the polyol modified by the following formula: -YZ n [In the formula, Y is Y 1 and Y 2 A 1+n valence base consisting of one or more selected from the group comprising, Y 1 This group is composed of one or more elements selected from the group consisting of 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 a hydrogen atom or an organic group having 1 to 30 carbon atoms in each instance). Y 2 This group is composed of one or more selected from the group consisting of a di- to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have substituents, a di- to tetravalent aromatic hydrocarbon ring which may have substituents, and a di- to tetravalent heterocycle which may have substituents. 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 of 1 or more and 3 or less.] is a compound substituted with a group represented by; the amine modifier is an amine skeleton, and the following formula: -X-Z n [X is a 1 + n-valent group composed of one or more selected from the group consisting of X 1 and X 2 is a group composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, -C(OR')R'-, and -C(OR')(-)2, -N(-)2 (wherein R' is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms in each occurrence).), X 1 is a group composed of one or more selected from the group consisting of an optionally substituted aliphatic hydrocarbon group having 2 to 4 carbon atoms, an optionally substituted hydrocarbon aromatic ring, and an optionally substituted heterocyclic ring, X 2 is a group composed of one or more selected from the group consisting of an optionally substituted aliphatic hydrocarbon group having 2 to 4 carbon atoms, an optionally substituted hydrocarbon aromatic ring, and an optionally substituted heterocyclic ring, 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 of 1 or more and 3 or less.] has one or more groups represented by, at least one -X-Z n is bonded to the nitrogen atom of the amine skeleton, and is a compound according to any one of items 1 to 6. [Item 8] Y of the polyol modifier is -O-Y 11 -, or -O-Y 11 -Y 21 -Y 12 -[[]] [wherein each symbol is independently in each occurrence, Y 11However, these are direct bonds, -C(=O)-, -C(=O)-NR'-, or -C(=S)-NR'-, Y 21 However, it is a hydrocarbon group having 1 to 40 carbon atoms, which may have substituents. Y 12 -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 product, The following formula: N(-XZ n ) p (New H) q -L 1 -[N(-XZ n ) r (New H) s -L 1 -] t -N(-XZ n ) p (New H) q [In the formula, X and Z are as described above, independently in each occurrence. L 1 This is a divalent aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms, which may be independently cleaved by oxygen atoms and / or sulfur atoms in each appearance. n is an integer between 1 and 3, independently of each occurrence. p is an integer between 0 and 2, independently in each occurrence. q is an integer between 0 and 2, independently in each occurrence. p+q is each N(-XZ n ) p (New H) q In this case, it is 2, r is either 0 or 1 independently in each occurrence. s is independently 0 or 1 in each occurrence. r+s is each N(-XZ n ) r (New H) s In this case, it is 1, The sum of all p and all r is 1 or greater. t is an integer between 0 and 10 (inclusive). A compound represented by, or The following formula: N(-XZ n ) p (New H) q -L 2 (-XZ n ) u [In the formula, X and Z are as described above, independently in each occurrence. L 2 This is a 1+u valent aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms, which may be cleaved by oxygen atoms and / or sulfur atoms. n is an integer between 1 and 3, which may be independently divided by oxygen atoms and / or sulfur atoms in each occurrence. p is an integer between 0 and 2, q is an integer between 0 and 2, p+q is 2, u is an integer between 1 and 3, The sum of p and u is 1 or greater. A repellent agent according to any one of items 1 to 7, which is a compound represented by [the formula shown]. [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 hydroxyl group-containing compound polymers. A repellent according to any one of items 1 to 8, wherein the amine is an organic amine. [Section 10] Polyols 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; It is at least one selected from the group consisting of polyglycerin, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymer, hydroxypropyl (meth)acrylate polymer, and hydroxybutyl (meth)acrylate polymer; The repellent according to any one of claims 1 to 9, wherein the amine is at least one selected from the group consisting of alkylenediamines, alkylentriamines, alkylenetetramines, and aromatic amines. [Section 11] The repellent according to any one of claims 1 to 10, wherein the cationic dispersant is a quaternary ammonium salt. [Section 12] The repellent according to any one of claims 1 to 11, wherein the biobase of the polyol-modified or amine-modified material is 20% or more. [Section 13] The repellent according to any one of claims 1 to 12, wherein the amine-modified material is a polyamide. [Section 14] The liquid-repellent compound is the polyol-modified compound, The polyol-modified product has a hydroxyl group in a polyglycerin with a degree of polymerization of 5 to 15, as shown in the following formula: -OC(=O)-Z [In the formula, Z is an alkyl group with 14 to 24 carbon atoms. A compound substituted with a group represented by , The repellent according to any one of claims 1 to 13, wherein the hydroxyl group substitution rate in the polyol modified product is 50% or more. [Section 15] A repellent agent as described in any one of items 1 to 14, for use in textile products or paper products. [Section 16] Products treated with any one of the repellents described in items 1 through 15. [Section 17] The products described in item 16, which are textile products or paper products. [Section 18] The product described in item 16 or 17, which is oil-resistant paper or water-resistant paper. [Section 19] A product described in any one of subheadings 16 to 18, which is a food packaging material or food container. [Section 20] A method for manufacturing a treated product, comprising the step of treating a substrate with a repellent described in any one of items 1 to 15. [Section 21] The manufacturing method according to item 20, wherein the aforementioned treatment is an internal additive treatment. [Effects of the Invention]

[0007] The repellent agent in this disclosure can impart good liquid repellency (particularly oil resistance) to paper products. [Modes for carrying out the invention]

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

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

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

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

[0012] <Repellent>

[0013] The repellent agent in this disclosure imparts liquid repellency (water repellency, oil repellency, oil resistance, and / or water resistance) to a substrate (e.g., a textile substrate, a paper substrate), and can function as at least one selected from the group consisting of water repellents, oil repellents, oil-resistant agents, and water-resistant agents. The repellent agent in this disclosure can impart good oil resistance (oil repellency) and / or water resistance (water repellency) to the substrate, and can, for example, impart good oil resistance and water resistance.

[0014] The repellent in this disclosure may be a water-dispersible repellent comprising a liquid-repellent compound selected from the group consisting of polyol-modified and amine-modified compounds, and a cationic dispersant.

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

[0016] [Volume abundance ratio of particles] The volume abundance of particles 1 μm or larger measured by laser diffraction scattering in the repellent of this disclosure may be 0.1% or more, 3% or more, 5% or more, 10% or more, or 15% or more, and may also 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, or 1.5% or less, or 0%, preferably 50% or less, or 30% or less. From the viewpoint of coating performance and dispersion stability, it is preferable that the volume abundance of particles 1 μm or larger measured by laser diffraction scattering is within the above range (particularly below the above upper limit). The method for achieving the above range for the volume abundance of particles 1 μm or larger measured by laser diffraction scattering is not limited, but for example, the particles in the raw material and / or dispersion can be finely ground using a pulverizer or homogenizer.

[0017] [Volume median diameter] The volume median diameter measured by laser diffraction scattering in the repellent of this disclosure may be 10 nm or more, 30 nm or more, 50 nm or more, or 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 this disclosure, the volume median diameter refers to the median diameter (D50) in the volume-based particle size distribution measured by laser diffraction scattering.

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

[0019] The anionic demand of an aqueous solution of a 0.1 g / L sample was measured using a particle charge meter (MUTEK PCD-04 manufactured by BTG) with a 1 / 1000 N potassium polyvinyl sulfonate solution, and the ionic charge density (cationic charge density) was calculated from the following formula (1). Alternatively, the cationic demand was measured in the same manner using a diallyldimethylammonium chloride solution instead of potassium polyvinyl sulfonate, and the ionic charge density (anionic charge density) was calculated from the following formula (1). Ionic charge density (μeq / g) = A / B (1) A: Cationic demand or anionic demand (μeq / L) B: Sample solution concentration (g / L)

[0020] [Polyol modifier] The polyol modifier in the present disclosure can adhere to a substrate and impart liquid repellency, for example, oil resistance and water resistance, to the substrate.

[0021] [Properties, etc.] The HD (n-hexadecane) contact angle of the polyol modifier 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, preferably 30° or more. The HD contact angle of the polyol modifier may be 100° or less, 90° or less, or 75° or less. When the polyol modifier has an HD contact angle of the above lower limit or more, it can impart good liquid repellency (especially oil repellency) to the substrate. The HD contact angle is the static contact angle of the spin-coated film of the polyol modifier 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 droplet adheres.

[0022] The water contact angle of the polyol-modified material may be 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 65° or more, 75° or more, 85° or more, 90° or more, or 100° or more, and may also be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. By having a water contact angle of the polyol-modified material above the lower limit of the above limits, good liquid repellency (especially water repellency) can be imparted to the substrate. The water contact angle is the static contact angle of the polyol-modified material 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.

[0023] The polyol-modified compound is preferably a compound having bio-based carbon. The degree of biobase is measured in accordance with ASTM D6866. The degree of biobase may be 20% or more, preferably 30% or more, more preferably 50% or more, even more preferably 60% or more, even more preferably 70% or more, and most preferably 80% or more or 90% or more, for example 100%. A high degree of biobase means that the amount of fossil resource-based materials, such as petroleum, used is small, and from this viewpoint, a higher degree of biobase in the polyol-modified compound is preferable.

[0024] The biodegradability of the polyol-modified material after 180 days is preferably 5% or more. Higher biodegradability is preferable as it reduces the environmental impact. The biodegradability of the polyol-modified material 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 material after 60 days is preferably 5% or more. Higher biodegradability is preferable as it reduces the environmental impact. The biodegradability of the polyol-modified material 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, and more preferably 60% or less. Such biodegradability may be as defined in JIS K 6953-1 or ASTM D6400.

[0025] [Structure etc.] The polyol modifiers in this disclosure do not necessarily have to contain any of the group selected from the group consisting of fluoroalkyl groups having 8 or more carbon atoms, perfluoroalkyl groups having 8 or more carbon atoms, fluoroalkyl groups having 4 or more carbon atoms, perfluoroalkyl groups having 4 or more carbon atoms, perfluoroalkyl groups, fluoroalkyl groups, and fluorine atoms. Even if the polyol modifiers do not contain these fluorine-containing groups, they can still impart liquid repellency to the substrate.

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

[0027] In this disclosure, the degree of polymerization refers to the average degree of polymerization. In this disclosure, the average degree of polymerization refers to polymerization obtained by measurement under the following conditions. In this disclosure, when the polyol-modified product is a polyglycerin-modified product obtained by modifying polyglycerin, the degree of polymerization of the polyol-modified product refers to the average degree of polymerization of the polyglycerin. The average degree of polymerization of polyglycerin is the average degree of polymerization (n) calculated from the hydroxyl value by the end-group analysis method. Specifically, the average degree of polymerization and the average molecular weight are calculated from the following formulas (Formula 1) and (Formula 2). (Formula 1) Average molecular weight = 74n+18 (Equation 2) Hydroxyl value = 56110(n+2) / average molecular weight The hydroxyl value in (Equation 2) above is a numerical value that serves as an indicator of the magnitude of the number of hydroxyl groups contained in polyglycerin. The hydroxyl value is calculated from the amount of potassium hydroxide required to neutralize the acetic acid necessary to acetylate the free hydroxyl groups contained in 1 g of polyglycerin, and is calculated in accordance with the "Standard Oil and Fats Analysis Test Method (I), 2003 Edition," compiled by the Japan Oil Chemists' Society. The hydroxyl value of the raw material polyglycerin can be measured according to the above standard oil and fat analysis test method, and the average degree of polymerization and average molecular weight of polyglycerin can be calculated from the above relationship.

[0028] In the case where the polyol-modified product in this disclosure is a polyvinyl alcohol-modified product obtained by modifying polyvinyl alcohol, the degree of polymerization of the polyol-modified product refers to the average degree of polymerization of the polyvinyl alcohol. The average degree of polymerization of polyvinyl alcohol can be measured in accordance with the JIS K 6726 polyvinyl alcohol test method.

[0029] In this disclosure, if the polyol-modified product is a polysaccharide-modified product obtained by modifying a polysaccharide, the degree of polymerization of the polyol-modified product refers to the average degree of polymerization of the polysaccharide. The average degree of polymerization of the polysaccharide can be analyzed as follows. The degree of polymerization is the number of monosaccharide units (fructose and glucose units) in the polysaccharide, and the average degree of polymerization is determined by taking the top peak among the peaks of each analytical result obtained by conventional analytical methods such as HPLC, GC, and HPAEC as the average degree of polymerization. For example, the measurement can be performed by using a column such as Shinwa Chemical's ULTRON PS-80N (8 × 300 mm) (solvent: water, flow rate: 0.5 ml / min, temperature: 50°C) or TOSOH's TSK-GEL G30000 PWXL (7.8 × 300 mm) (solvent: water, flow rate: 0.5 ml / min, temperature: 50°C) and a differential refractometer as the detector.

[0030] The polyol-modified compounds may be low molecular weight (e.g., weight-average molecular weight less than 1500, less than 1000, or 500 or less) and / or high molecular weight. The weight-average molecular weight of the polyol-modified product may be 100 or more, 200 or more, 300 or more, 400 or more, 500 or more, 1000 or more, 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more, and may also be 3000000 or less, 1000000 or less, 750000 or less, 500000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 10000 or less, 9000 or less, 8000 or less, 7000 or less, 6000 or less, 5000 or less, 3000 or less, 2000 or less, 1000 or less, or 500 or less.

[0031] The substitution rate of hydroxyl groups in the polyol-modified product may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 100%, preferably 10% or more, for example 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, particularly 80% or more, and may also be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, or 15% or less, for example 95% or less. Here, the "substitution rate" means the proportion (mol%) of hydroxyl groups derived from the polyol that are modified, and may mean the proportion (mol%) of those modified by monovalent hydrocarbon groups having 1 to 40 carbon atoms or monovalent polysiloxane groups that may have substituents.

[0032] The remaining percentage of hydroxyl groups in the polyol-modified product may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, for example, 5% or more, or 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, 15% or less, or 5% or less, for example, 50% or less, 30% or less, or 10% or less. Here, "remaining percentage" means the proportion (mol%) of hydroxyl groups derived from the polyol that are not modified.

[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 also be 1000 or less, 750 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less. Here, the modifying groups are preferably monovalent hydrocarbon groups or monovalent polysiloxane groups which may have substituents.

[0034] The equivalent weight of the modifying group 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 also be 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, or 400 or less. This is the value obtained by dividing the weight-average molecular weight of the polyol-modified product by the number of modifying groups. Here, the modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have substituents.

[0035] The polyol-modified product is one in which 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 substituents. From the viewpoint of improving liquid repellency, the polyol-modified product may have a structure in which the polyol is modified with an alkyl group having 6 to 40 carbon atoms (for example, an unsubstituted alkyl group having 6 to 40 carbon atoms), which may have substituents.

[0036] (A monovalent hydrocarbon group which may have substituents) The hydrocarbon group modified to the polyol in the polyol-modified product may be a monovalent hydrocarbon group that may have substituents.

[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 an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group (alkyl group), is preferred. 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, preferably 6 or more, 10 or more, 12 or more, or 16 or more, and may also be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, 25 or less, or 20 or less.

[0039] The hydrocarbon group may have a substituent, but is preferably unsubstituted. Examples of the substituent include -OR', -N(R')2, -COOR', and a halogen atom, etc. (wherein, R' is, independently at each occurrence, a hydrogen atom or 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 an active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the hydrocarbon group having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less. For example, the hydrocarbon group may have 1 to 3 (e.g., 1) -OR' (particularly -OH) as a substituent (e.g., other than at the terminal).

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

[0041] The polysiloxane group has the following formula: -[-Si(R s )2-O-] a - [wherein, R s is, independently at each occurrence, a hydrocarbon group having 1 to 40 carbon atoms or a reactive group, a is an integer of 5 or more and 10000 or less.] It may also be represented by

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

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

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

[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 also be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, more preferably 25 or less.

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

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

[0048] R is a hydrocarbon group with 1 to 5 carbon atoms in the polysiloxane group. s The amount is R s The amount of the total may be 20 mol% or more, 40 mol% or more, 60 mol% or more, or 80 mol% or more, preferably 50 mol% or more, and may also be 100 mol% or less, 90 mol% or less, 80 mol% or less, or 70 mol% or less. For example, R s It is also possible that 50 mol% or more of the total number of groups are methyl groups or ethyl groups (especially methyl groups).

[0049] R is a hydrocarbon group with 6 to 40 carbon atoms in the polysiloxane group. s The amount is R s The amount of the total may be 3 mol% or more, 10 mol% or more, 20 mol% or more, or 30 mol% or more, and may also be 100 mol% or less, 90 mol% or less, 80 mol% or less, or 70 mol% or less.

[0050] In the polysiloxane group, the reactive group R s The amount is R s The amount may be 5 mol% or more, 10 mol% or more, 20 mol% or more, or 30 mol% or more relative to the total, and may also be 50 mol% or less, 40 mol% or less, 30 mol% or less, or 20 mol% or less.

[0051] R s The elements may be introduced randomly or in blocks, but random is preferred.

[0052] The terminal structure of the polysiloxane group described above is not limited to, but -ORs , -Si(R s ) may be third class. R of terminal structure s It may have one or more reactive groups. Examples of reactive groups are as described above, and may be, for example, at least one selected from the group consisting of epoxy rings, hydroxyl groups, (meth)acrylic groups, and carboxyl groups.

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

[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 [wherein, R s is, independently at each occurrence, a hydrocarbon group or a reactive group having 1 to 40 carbon atoms, and the terminal R s has one or more reactive groups, R s in the total of the R groups, 50 mol% or more is a methyl group, L s1 is a hydrocarbon group having 1 to 20 carbon atoms, a is 5 or more and 10000 or less. ], JPEG0007897514000001.jpg31109[wherein, 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. are exemplified.

[0055] (-Y-Z n ) In the polyol-modified product in the present disclosure, one or more hydroxy groups of the polyol are represented by the following formula: -Y-Z n [wherein, Y is a 1 + n-valent group composed of one or more selected from the group consisting of Y 1 and Y 2 ; Y 1 is a group composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR’)-, -S-, -S(=O)2-, -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 (for example, 1 to 20, 1 to 10, or 1 to 4 carbon atoms) (for example, a hydrocarbon group, particularly an aliphatic hydrocarbon group).), Y 2 is a group composed of one or more selected from the group consisting of an optionally substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms and 2 to 4 valences, an optionally substituted hydrocarbon aromatic ring, and an optionally substituted heterocyclic ring having 2 to 4 valences, Z is a monovalent hydrocarbon group having 1 to 40 carbon atoms, or a monovalent polysiloxane group, which may have substituents. n is an integer between 1 and 3 (inclusive). It is substituted with a group represented by .

[0056] (Y) Y is Y 1 and Y 2 A 1+n valence base consisting of one or more selected from the group comprising, Y 1 This is a group composed of one or more selected from the group consisting of direct bonds, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, -C(OR')R'-, and -C(OR')(-)2, -N(-)2 (wherein R' 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, especially an aliphatic hydrocarbon group)) in each occurrence. Y 2 This group is composed of one or more selected from the group consisting of a di- to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have substituents, a di- to tetravalent hydrocarbon aromatic ring which may have substituents, and a di- to tetravalent heterocycle which may have substituents.

[0057] n is the number of Z elements that combine with Y, and can be an integer between 1 and 3. n can be 1 or greater, 2 or greater, or 3 or greater, and can also 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 also be 3000 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less.

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

[0060] Y 1 This is a directly bonded or divalent or more group. 1 The valence of Y may be 2-4, 2-3, or 2. 1 It is preferable that the bonding is not solely direct.

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

[0062] Y 1 It may consist of one or more selected from the group consisting of direct bonds, -O-, -C(=O)-, -S(=O)2-, -NR'-, -C(OR')R'-, and -C(OR')(-)2 (wherein R' 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, especially an aliphatic hydrocarbon group)). 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')(-)2nd class (In the formula, R' is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms) in each instance.) These are some examples.

[0063] ○ Y 2 Y 2 This is a linker of an optionally substituted hydrocarbon, an optionally substituted hydrocarbon aromatic ring, or an optionally substituted heterocycle.

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

[0065] Y 2 Y is a group with two or more valent values. 2 The valence may be, for example, 2-4, 2-3, or 2.

[0066] Y 2 The number of carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, and may also be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[0067] Y 2 It consists of one or more selected from the group consisting of a di- to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have substituents, a di- to tetravalent hydrocarbon aromatic ring which may have substituents, and a di- to tetravalent heterocycle which may have substituents.

[0068] A divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or linear hydrocarbon group. A divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The number of carbon atoms in a divalent to 40 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more, and may also be 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less. The valency of the aliphatic hydrocarbon group may be 2 or more, 3 or more, or 4, and may be 4 or less, 3 or less, or 2.

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

[0070] Examples of divalent to tetravalent hydrocarbon aromatic rings include groups obtained by removing 2 to 4 hydrogen atoms from hydrocarbon aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthacene), pentacene, pyrene, and coronene. The number of ring constituent atoms of the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valency of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0071] The hydrocarbon aromatic ring may have substituents. Examples of substituents include -R', -OR', -N(R')2, -COOR', and halogen atoms (wherein R' is independently a hydrogen atom or an organic group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms (e.g., a hydrocarbon group, especially an aliphatic hydrocarbon group)). The substituents may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the hydrocarbon aromatic ring having substituents, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0072] The 2-4 valent heterocycle may be an aliphatic group or an aromatic group. Examples of 2-4 valent heterocycles include groups obtained by removing 2-4 hydrogen atoms from pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, etc. The number of ring constituent atoms of the heterocycle is 3-20, 4-16, or 5-12, preferably 5-12. The valency of the heterocycle may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0073] The heterocycle may have substituents. Examples of substituents include -R', -OR', -N(R')2, -COOR', and halogen atoms (wherein R' is independently a hydrogen atom or an organic group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms (e.g., a hydrocarbon group, especially an aliphatic hydrocarbon group)). The substituents may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In a substituted heterocycle, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, for example, 65 mol% or more, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less.

[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.] These are some examples.

[0075] Y 2 Specific examples include: -(CH2) p -(p is 1-40, 1-20, or 1-10), A linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and unsaturated bonds. Hydrocarbon groups having a branched structure with 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH2) q -Cy-(CH2) r -(q and r are each independently between 0 and 20, for example between 1 and 10, and Cy is a hydrocarbon aromatic ring or heterocycle) These are some examples.

[0076] (Example of Y) Let's explain the example of Y. In the following, R' is independently a hydrogen atom or an organic group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) (e.g., a hydrocarbon group, especially an aliphatic hydrocarbon group) in each instance.

[0077] An example of Y is when Y is divalent, -Y 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 - are some examples.

[0078] An example of Y is when Y is trivalent, -Y 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 [[ID=​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​2 -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 [[ID=​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​ A preferred example of Y is -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, These are some examples.

[0081] (Example of a favorable Y) Preferably, Y -OY 11 -, or -OY 11 -Y 21 -Y 12 - [In the formula, each symbol is independent in each occurrence.] Y 11 However, these are direct bonds, -C(=O)-, -C(=O)-NR'-, or -C(=S)-NR'-, Y 21 However, it is a hydrocarbon group having 1 to 40 carbon atoms, which may have substituents. 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. That's fine.

[0082] Y 11 It is a non-hydrocarbon linker, and is either directly bonded or a divalent or more valent 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 also be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more.

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

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

[0086] Y 21 The number of carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, and may also be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[0087] Here, the hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or linear hydrocarbon group, and may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The hydrocarbon group may have substituents. Examples of substituents 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, especially an aliphatic hydrocarbon group) in each occurrence). The substituents may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In a substituent hydrocarbon group, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0088] Y 21 Specific examples include: -(CH2) p -(p is 1-40, 1-20, or 1-10), A linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and unsaturated bonds. Hydrocarbon groups having a branched structure with 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH2) q -Cy-(CH2) r -(q and r are each independently between 0 and 20, for example between 1 and 10, and Cy is a hydrocarbon aromatic ring or heterocycle) These are some examples.

[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 having 1 to 40 carbon atoms, or a monovalent polysiloxane group, which may have substituents, and the above-described explanations for (monovalent hydrocarbon group, which may have substituents) and (monovalent polysiloxane group) are applied. 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 unsaturated bonds, and the number of unsaturated bonds is preferably 4 or less, 2 or less, or 1. The substituent is preferably an OH (hydroxyl group).

[0091] [Other modifying groups] The hydroxyl group of the polyol is -YZ nIt may be substituted with other modifying groups. Examples of modifying groups include anionic groups and / or cationic groups.

[0092] Examples of anionic groups include monomers having a carboxyl group, a sulfonic acid group, or a phosphate group.

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

[0094] The cationic group is an amino group, preferably a tertiary amino group and a quaternary amino group. In a tertiary amino group, the two groups bonded to the nitrogen atom are preferably the same or different aliphatic group having 1 to 5 carbon atoms (especially alkyl groups), an aromatic group having 6 to 20 carbon atoms (aryl groups), or an aromatic aliphatic group having 7 to 25 carbon atoms (especially aralkyl groups, such as benzyl groups (C6H5-CH2-)). In a quaternary amino group, the three groups bonded to the nitrogen atom are preferably the same or different aliphatic group having 1 to 5 carbon atoms (especially alkyl groups), an aromatic group having 6 to 20 carbon atoms (aryl groups), or an aromatic aliphatic group having 7 to 25 carbon atoms (especially aralkyl groups, such as benzyl groups (C6H5-CH2-)). In both tertiary and quaternary amino groups, the remaining group bonded to the nitrogen atom may have a carbon-carbon double bond. The cationic group may also be in the form of a salt.

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

[0096] [Method for producing polyol-modified compounds] Polyol-modified products may also be produced by reacting a modifying agent having a modifying group (or a precursor structure of a modifying group) with the hydroxyl group of a polyol.

[0097] (Polyol) A polyol is a compound having two or more hydroxyl groups and is a compound that serves as a raw material for polyol-modified products. A polyol is a compound that has two or more hydroxyl groups in its molecule. Polyols may be aliphatic or aromatic, but are preferably aliphatic.

[0098] The polyol may have ether bonds. Preferably, the polyol may have two or more ether bonds. Specifically, the polyol is preferably a compound having two or more hydroxyl groups and two or more ether bonds. In other words, the polyol is preferably a polyether having two or more hydroxyl groups.

[0099] If the polyol is a polymer, the repeating structure of the monomer units may contain hydroxyl groups and ether bonds.

[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, 30000 or more, 300000 or more, 300000 or less, 1000000 or less, 750000 or less, 500000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 10000 or less, 5000 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 hydroxyl groups in a polyol may be 2 or more, 5 or more, 7 or more, 10 or more, 15 or more, 30 or more, 50 or more, or 100 or more, and may also be 3000 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less.

[0102] The hydroxyl group equivalent of a polyol may be 20 or more, 40 or more, 60 or more, 80 or more, 100 or more, 120 or more, or 150 or more, and may also be 1000 or less, 800 or less, 600 or less, 400 or less, 200 or less, 100 or less, or 75 or less. The hydroxyl group equivalent of a polyol is the value obtained by dividing the weight-average molecular weight of the polyol by the number of hydroxyl groups.

[0103] Polyols may be natural products. These natural products may be high molecular weight natural products, low molecular weight natural products, or derivatives thereof. The above natural products also include compounds converted from microorganisms. Examples of polyols include monosaccharides, oligosaccharides, polysaccharides, sugar alcohols (reducing sugars), hydroxy acids, amino acids, vitamins, flavonols, hydroxy hydrocarbons, hydroxy group-containing compound polymers, polyether polyols, polymer polyols, polyester polyols, and other polyols.

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

[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, and lactitol.

[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, and gluconic acid.

[0109] Examples of amino acids include glucosamine.

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

[0111] Examples of flavonols include catechins, quercetin, and anthocyanins.

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

[0113] Examples of hydroxyl group-containing compound polymers include polyglycerin, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymer, hydroxypropyl (meth)acrylate polymer, and hydroxybutyl (meth)acrylate polymer.

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

[0115] Examples of polymer polyols include compounds obtained by polymerizing a polyether polyol with an ethylenically unsaturated monomer in a polyether polyol. Examples of the ethylenically unsaturated monomer include acrylonitrile and styrene.

[0116] Examples of polyester polyols include compounds obtained by dehydration condensation of a compound having two or more carboxyl groups and a compound having two or more hydroxyl groups. Examples of compounds having two or more carboxyl groups include terephthalic acid, isophthalic acid, phthalic acid, methylphthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, succinic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, and their acid anhydrides. Examples of compounds having two or more hydroxyl groups include ethylene glycol, propylene glycol, propanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and polymers thereof.

[0117] (Modifier) The modifier is preferably a compound that is reactive with the polyol and has a monovalent hydrocarbon group having 1 to 40 carbon atoms, which may have substituents, or a monovalent polysiloxane group, as described above.

[0118] Examples of modifiers 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 Halogenated 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] In the above-described structure of the modifier, Z may be replaced with any group constituting the modifying group. For example, Z may be a monovalent hydrocarbon group having 1 to 40 carbon atoms, which may have substituents, or a group having a monovalent polysiloxane group. For example, Z may be -YZ. n That is also acceptable.

[0120] Polyol-modified compounds may also be synthesized by reacting a polyol with a modifier. For example, a polyol-modified compound can be synthesized by reacting a modifier, such as an acid halogen compound, acid anhydride, or carboxylic acid, with the hydroxyl group of a polyol to form an ester bond. Alternatively, a polyol-modified compound can be produced by reacting a modifier, such as a halide or epoxy compound, with the hydroxyl group of a polyol to form an ether bond. The reaction conditions between the polyol and the modifier can be appropriately designed by those skilled in the art, depending on the desired product, by using a catalyst (e.g., an acid catalyst or a base catalyst), a condensing agent, etc.

[0121] [Amine-modified] The amine-modified material in this disclosure can adhere to a substrate and impart liquid-repellent properties to the substrate.

[0122] [Characteristics, etc.] The amine-modified compounds in this disclosure exhibit excellent dispersibility in liquid media due to their structure, and the repellents in this disclosure can have stable performance. In the case of repellents using polymer-type compounds as active ingredients, the molecular weight distribution is broad and tends to contain a relatively large amount of impurity components. On the other hand, amine-modified compounds can be reduced in molecular weight, narrowing (single-molecule) the molecular weight distribution, and thus can have good performance.

[0123] The HD (n-hexadecane) contact angle of the amine-modified material 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 also be 100° or less, 90° or less, or 75° or less. By having an HD contact angle of the amine-modified material greater than or equal to the lower limit above, good liquid repellency (especially oil repellency) can be imparted to the substrate. The HD contact angle is the static contact angle of the amine-modified material with respect to the 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 dropping.

[0124] The water contact angle of the amine-modified material may be 35° or higher, 40° or higher, 45° or higher, 50° or higher, 55° or higher, 65° or higher, 75° or higher, 85° or higher, 90° or higher, or 100° or higher, and may also be 160° or lower, 140° or lower, 130° or lower, 120° or lower, 110° or lower, 100° or lower, or 90° or lower. By having a water contact angle of the amine-modified material above the lower limit of the above limits, good liquid repellency (especially water repellency) can be imparted to the substrate. The water contact angle is the static contact angle of the amine-modified material 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.

[0125] The amine-modified compound is preferably a compound having carbon of bio-based origin. The degree of bio-basedness is measured in accordance with ASTM D6866. The degree of bio-basedness may be 20% or more, preferably 30% or more, more preferably 50% or more, even more preferably 60% or more, even more preferably 70% or more, and most preferably 80% or more or 90% or more, for example 100%. A high degree of bio-basedness means that the amount of fossil resource-based materials, such as petroleum, used is small, and from this viewpoint, a higher degree of bio-basedness of the amine-modified compound is preferable.

[0126] The biodegradability of the amine-modified product after 180 days is preferably 5% or more. Higher biodegradability is preferable as it reduces the environmental impact. 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. Higher biodegradability is preferable as it reduces the environmental impact. 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, and more preferably 60% or less. Such biodegradability may be as defined in JIS K 6953-1 or ASTM D6400.

[0127] The melting point of the amine-modified product may be 30°C or higher, 40°C or higher, 60°C or higher, 80°C or higher, 100°C or higher, or 120°C or higher, preferably 40°C or higher, and may also be 200°C or lower, 150°C or lower, 130°C or lower, 120°C or lower, 110°C or lower, 100°C or lower, 80°C or lower, or 50°C or lower. The amine-modified product may not have a melting point.

[0128] [Structure etc.] The amine modifier in this disclosure does not necessarily have to contain any of the 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 modifier does not contain these fluorine-containing groups, it can still impart liquid repellency to the substrate.

[0129] The molecular weight of the amine-modified product may be 200 or more, 300 or more, 350 or more, 400 or more, 500 or more, 550 or more, or 750 or more, and may also be 3000 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 900 or less, 800 or less, 750 or less, or 500 or less.

[0130] The amine-modified compounds in this disclosure do not necessarily have active hydrogen-containing groups. Examples of active hydrogen-containing groups include amino groups (amino groups not adjacent to a carbonyl group, e.g., primary or secondary amino groups), hydroxyl groups, and carboxyl groups. In particular, the amine-modified compounds in this disclosure do not necessarily have primary or secondary amino groups not adjacent to a carbonyl group.

[0131] The amine-modified product in this disclosure may be a polyamide having multiple amide groups, for example, a polyamide in which multiple modifying groups (e.g., Z as described below) are modified via amide groups to an amine (a starting amine compound, e.g., a polyamine). Here, the amide may include amide moieties contained in urethane groups, urea groups, imides, etc.

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

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

[0134] (A monovalent hydrocarbon group which may have substituents) The hydrocarbon group modified to the amine in the amine-modified product may be a monovalent hydrocarbon group that may have substituents.

[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 an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group (alkyl group), is preferred. 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, preferably 6 or more, 10 or more, 12 or more, or 16 or more, and may also be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, 25 or less, or 20 or less.

[0137] The hydrocarbon group may have substituents, but it is preferable that it be unsubstituted. Examples of substituents include -OR', -N(R')2, -COOR', and halogen atoms (wherein R' is independently a hydrogen atom or an organic group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms (e.g., a hydrocarbon group, especially an aliphatic hydrocarbon group)). The substituent may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In a hydrocarbon group having substituents, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less. For example, a hydrocarbon group may have 1 to 3 (e.g., 1) -OR' (especially -OH) substituents (e.g., not at the terminal ends).

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

[0139] The polysiloxane group is represented by the following formula: -[-Si(R s )2-O-] a - [In the formula, R s In each instance, it is independently a hydrocarbon group or reactive group having 1 to 40 carbon atoms. 'a' is an integer between 5 and 10000 (inclusive). It may also be represented as follows.

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

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

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

[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 also be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, more preferably 25 or less.

[0144] Examples of reactive groups are groups having a functional group (e.g., hydroxyl group, amino group, mercapto group, epoxy group, carboxyl group, halogen-substituted alkyl group, vinyl group, (meth)acrylic group, (meth)acryloyloxy group, and (meth)acrylamide group, hydrogen atom directly bonded to a silicon atom, etc.). These functional groups may be directly bonded to a silicon atom or to an organic group directly bonded to a silicon atom. The organic group may be a hydrocarbon group, for example, an alkylene group or a divalent aromatic group. The hydrocarbon group may have 2 to 12 carbon atoms, and alkylene groups with 2 to 10 carbon atoms are preferred. Divalent aromatic groups with 6 to 12 carbon atoms are preferred. The reactive group may be a group selected from the group consisting of hydroxyl group, epoxy ring, carboxyl group, (meth)acrylic group, and amino group, for example, at least one selected from the group consisting of epoxy ring, hydroxyl group, (meth)acrylic group, and carboxyl group.

[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, preferably 10 or more, and may also be 10000 or less, 7500 or less, 5000 or less, 3000 or less, 1500 or less, 1000 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less, preferably 500 or less.

[0146] R is a hydrocarbon group with 1 to 5 carbon atoms in the polysiloxane group. s The amount is R s The amount of the total may be 20 mol% or more, 40 mol% or more, 60 mol% or more, or 80 mol% or more, preferably 50 mol% or more, and may also be 100 mol% or less, 90 mol% or less, 80 mol% or less, or 70 mol% or less. For example, R s It is also possible that 50 mol% or more of the total number of groups are methyl groups or ethyl groups (especially methyl groups).

[0147] R is a hydrocarbon group with 6 to 40 carbon atoms in the polysiloxane group. s The amount is Rs The amount of the total may be 3 mol% or more, 10 mol% or more, 20 mol% or more, or 30 mol% or more, and may also be 100 mol% or less, 90 mol% or less, 80 mol% or less, or 70 mol% or less.

[0148] In the polysiloxane group, the reactive group R s The amount is R s The amount may be 5 mol% or more, 10 mol% or more, 20 mol% or more, or 30 mol% or more relative to the total, and may also be 50 mol% or less, 40 mol% or less, 30 mol% or less, or 20 mol% or less.

[0149] R s The elements may be introduced randomly or in blocks, but random is preferred.

[0150] The terminal structure of the polysiloxane group described above is not limited to, but -OR s , -Si(R s ) may be third class. R of terminal structure s It may have one or more reactive groups. Examples of reactive groups are as described above, and may be at least one selected from the group consisting of epoxy rings, hydroxyl groups, (meth)acrylic groups, and carboxyl groups.

[0151] The polysiloxane group may have a linker, and the amine and the polysiloxane group may be bonded via the linker. Such a linker may be, but is not limited, a hydrocarbon group having 1 to 40 (e.g., 1 to 20) carbon atoms that may be interrupted by an oxygen atom, such as 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 In each occurrence, independently, is a hydrocarbon group or reactive group having 1 to 40 carbon atoms, with terminal R s It has one or more reactive groups, R s More than 50 mol% of the total number of groups are methyl groups. L s1 It is a hydrocarbon group having 1 to 20 carbon atoms. a is between 5 and 10000. TIFF0007897514000002.tif31109[In the formula, a represents an integer between 0 and 150, b represents an integer between 1 and 150, (a+b) is between 5 and 200, and n is an integer between 0 and 36.] These are some examples.

[0153] For example, amine-modified compounds Amine skeleton, and The following formula: -XZ n [In the formula, X is a direct bond or a 1+n valence group, Z is a monovalent hydrocarbon group having 1 to 40 carbon atoms, or a monovalent polysiloxane group, which may have substituents. n is an integer between 1 and 3 (inclusive). It has one or more bases represented by, At least one -XZ n However, it is bonded to the nitrogen atom of the amine skeleton.

[0154] (Amine skeleton) The amine-modified compounds in this disclosure have an amine skeleton. The amine skeleton is obtained by removing a predetermined number of atoms or groups of atoms (e.g., hydrogen) from an amine compound and has one or more amino groups having a predetermined number of bonds (valence). The amino groups in the amine skeleton refer to groups selected from the group consisting of -NH2, -NH-, and -N(-)2, and also include amino groups adjacent to carbonyl groups contained in amide groups, urethane groups, urea groups, imides, etc. The amine skeleton may be any aliphatic or aromatic group having one or more amino groups, and the presence of heteroatoms other than nitrogen is not excluded.

[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 also be 2800 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 600 or less, 450 or less, 300 or less, or 250 or less.

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

[0157] The amine skeleton has one or more amino groups. The amino groups are 1-3 valent amino groups, and are selected from the group consisting of -NH2, -NH-, and -N(-)2. The number of amino groups in the amine skeleton may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, preferably 2 or more, and may also be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1.

[0158] The amine skeleton has hydrocarbon groups (aliphatic hydrocarbon groups or aromatic hydrocarbon groups). The hydrocarbon groups may be cyclic, branched, or linear. The hydrocarbon groups may be saturated or unsaturated (e.g., saturated). Here, the hydrocarbon groups may be cleaved by oxygen atoms and / or sulfur atoms, or they may consist only of carbon atoms, nitrogen atoms, and hydrogen atoms. The hydrocarbon groups may be hydrocarbon groups that are cleaved by oxygen atoms and / or sulfur atoms (e.g., linear saturated aliphatic hydrocarbon groups or aromatic hydrocarbon groups having 1-2 hydrocarbon aromatic rings), or they may be general hydrocarbon groups (e.g., linear saturated aliphatic hydrocarbon groups or aromatic hydrocarbon groups having 1-2 hydrocarbon aromatic rings). When the hydrocarbon groups are cleaved by oxygen atoms and / or sulfur atoms, they have an ether, thioether, polyether, or polythioether structure. The number of hydrocarbon groups in the amine skeleton may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, and may also be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1.

[0159] The amine skeleton may consist of a 1-3 valent amino group and a chain-like saturated aliphatic hydrocarbon group or aromatic hydrocarbon group, which may be cleaved by an oxygen atom and / or a sulfur atom.

[0160] The molar ratio (C / N ratio) of carbon atoms to nitrogen atoms in the amine skeleton may be 1 or more, 2 or more, 2.5 or more, 3 or more, 3.5 or more, or 4 or more, and may also be 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3.5 or less, 3 or less, 2.5 or less, or 2 or less, preferably 6 or less or 4 or less.

[0161] (-XZ n ) The amine-modified product in this disclosure is given by the following formula: -XZ n [In the formula, X is a direct bond or a 1+n valence group, Z is a monovalent hydrocarbon group having 1 to 40 carbon atoms, or a monovalent polysiloxane group, which may have substituents. n is an integer between 1 and 3 (inclusive). It has one or more bases represented by, At least one -XZ n However, it is bonded to the nitrogen atom of the amine skeleton.

[0162] The amine-modified compound 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, preferably 2 or more, and may also be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1.

[0163] At least one -XZ in the amine-modified product n However, it is bonded to the nitrogen atom of the amine skeleton. All -XZ in the amine modified product n Of the number of -XZ atoms bonded to the nitrogen atom of the amine skeleton n The proportion of these may be 10% or more, 30% or more, 60% or more, 80% or more, or 100%, and may also be 75% or less, 50% or less, or 25% or less. -XZ that is not bonded to the nitrogen atom of the amine skeleton. n It bonds to other groups (e.g., hydrocarbon groups) on the amine skeleton.

[0164] (X) X is either a direct bond or a 1+n valent group, preferably a 1+n valent group. X functions as a linker connecting the amine skeleton to n Zs.

[0165] n is the number of Z elements that combine with X, and can be an integer between 1 and 3. n can be 1 or greater, 2 or greater, or 3 or greater. n can be 3 or less, 2 or less, or 1 or less, for example, 2 or less.

[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 also 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 amide groups, urea groups, urethane groups, and imides, or X may form one or more selected from the group consisting of amide groups, urea groups, urethane groups, and imides 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 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms).] Examples include the following. X is preferably bonded to the nitrogen atom in the amine skeleton via a -(C=O)- group.

[0169] X can be 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 with 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 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, especially an aliphatic hydrocarbon group).] It may be a 1+n valence base composed of one or more elements selected from the group consisting of the following:

[0170] X is X 1 and X 2 A 1+n valence base consisting of one or more selected from the group comprising, X 1 This is a group composed of one or more selected from the group consisting of direct bonds, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, -C(OR')R'-, and -C(OR')(-)2, -N(-)2 (wherein R' 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, especially an aliphatic hydrocarbon group)) in each occurrence. X 2 This is a group composed of one or more selected from the group consisting of a di-tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a di-tetravalent aromatic hydrocarbon ring, and a di-tetravalent heterocycle. It may be a 1+n valent group consisting of one or more selected from the group comprising the above. In this specification, the group referred to as X has the amine skeleton on the left and is bonded to Z on the right.

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

[0172] X 1 X is a directly bonded or divalent or more group. 1 The valence of X may be 2-4, 2-3, or 2. 1 It is preferable that the bonding is not solely direct.

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

[0174] X 1 It may consist of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, -C(OR')R'-, -C(OR')(-)2, -N(-)2 (wherein R' 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, especially an aliphatic hydrocarbon group) in each occurrence). 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' 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, especially an aliphatic hydrocarbon group) in each instance.] This is one example. Note that X 1 If a nitrogen atom is bonded to a nitrogen atom of the amine skeleton, that nitrogen atom is considered part of the amine skeleton (amino group).

[0175] ○ X 2 X 2 This is a linker of an optionally substituted hydrocarbon, an optionally substituted hydrocarbon aromatic ring, or an optionally substituted heterocycle.

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

[0177] X 2 X is a group with two or more valent values. 2 The valence may be, for example, 2-4, 2-3, or 2.

[0178] X 2 The number of carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, and may also be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[0179] X 2 It consists of one or more selected from the group consisting of a di- to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have substituents, a di- to tetravalent hydrocarbon aromatic ring which may have substituents, and a di- to tetravalent heterocycle which may have substituents.

[0180] A divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or linear hydrocarbon group. A divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The number of carbon atoms in a divalent to 40 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more, and may also be 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less. The valency of the aliphatic hydrocarbon group may be 2 or more, 3 or more, or 4, and may be 4 or less, 3 or less, or 2.

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

[0182] Examples of divalent to tetravalent hydrocarbon aromatic rings include groups obtained by removing 2 to 4 hydrogen atoms from hydrocarbon aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthacene), pentacene, pyrene, and coronene. The number of ring constituent atoms of the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valency of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0183] The hydrocarbon aromatic ring may have substituents. Examples of substituents include -R', -OR', -N(R')2, -COOR', and halogen atoms (wherein R' is independently a hydrogen atom or an organic group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms (e.g., a hydrocarbon group, especially an aliphatic hydrocarbon group)). The substituents may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the hydrocarbon aromatic ring having substituents, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0184] The 2-4 valent heterocycle may be an aliphatic group or an aromatic group. Examples of 2-4 valent heterocycles include groups obtained by removing 2-4 hydrogen atoms from pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, etc. The number of ring constituent atoms of the heterocycle is 3-20, 4-16, or 5-12, preferably 5-12. The valency of the heterocycle may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

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

[0187] X 2 Specific examples include: -(CH2) p -(p is 1-40, 1-20, or 1-10), A linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and unsaturated bonds. Hydrocarbon groups having a branched structure with 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH2) q -Cy-(CH2) r -(q and r are each independently between 0 and 20, for example between 1 and 10, and Cy is a hydrocarbon aromatic ring or heterocycle) These are some examples.

[0188] Example of X Let's explain the example of X. In the following, R' is independently a hydrogen atom or an organic group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) (e.g., a hydrocarbon group, especially an aliphatic hydrocarbon group) in each instance.

[0189] An example of X is when X is divalent, -X 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. are examples.

[0190] An example of X is when X is trivalent, -X 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 -) 2nd place is an example.

[0191] An example of X is when X is tetravalent, -X 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; and others are examples.

[0192] A preferred example of X is -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, Examples include the above. In the amine-modified product, it is preferable that one or more X atoms have a -(C=O)- 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 However, each appearance is independent, direct binding, -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, or -C(=O)-NR'- -C(=O)-NR'-C(=O)- (In the formula, R' is independently a hydrogen atom or 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, especially an aliphatic hydrocarbon group) in each instance.) And, X 2 This is a divalent to tetravalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, or a divalent aromatic group (e.g., a divalent phenyl group, a divalent triazole group). This is a group represented by [formula]. This allows for good liquid repellency to be imparted to the substrate.

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

[0195] (Z) Z is a monovalent hydrocarbon group having 1 to 40 carbon atoms, which may have substituents, or a monovalent polysiloxane group, and the explanations for (monovalent hydrocarbon group, which may have substituents) and (monovalent polysiloxane group) described above are applied.

[0196] [Examples of amine-modified compounds] (Amine-modified example 1) An example of an amine-modified compound is shown below: N(-XZ n ) p (New H) q -L 1 -[N(-XZ n ) r (New H) s -L 1 -] t -N(-XZn ) p (New H) q [In the formula, X is, independently in each occurrence, a direct bond or a 1+n valence base. Z is a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have substituents, independently in each instance. L 1 This is a divalent aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms, which may be independently cleaved by oxygen atoms and / or sulfur atoms in each appearance. n is an integer between 1 and 3, independently of each occurrence. p is an integer between 0 and 2, independently in each occurrence. q is an integer between 0 and 2, independently in each occurrence. p+q is each N(-XZ n ) p (New H) q In this case, it is 2, r is either 0 or 1 independently in each occurrence. s is independently 0 or 1 in each occurrence. r+s is each N(-XZ n ) r (New H) s In this case, it is 1, The sum of all p and all r is 1 or greater. t is an integer between 0 and 10 (inclusive). Examples of compounds represented by (Amine Modified Compound Example 1) include the following.

[0197] In Amine Modification Example 1, the details of X, Z, and n are as described above.

[0198] In amine-modified example 1, L 1 L is a divalent aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms, which may be cleaved by oxygen atoms and / or sulfur atoms, and may be a cyclic, branched, or linear hydrocarbon group, preferably a linear hydrocarbon group or an aromatic hydrocarbon. 1As an example, the hydrocarbon group described above in the explanation of the [amine skeleton] may be used, and the hydrocarbon group may be divided by an oxygen atom and / or a sulfur atom, or it may consist only of a carbon atom, a nitrogen atom, and a hydrogen atom. 1 This may be, for example, a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1-2 hydrocarbon aromatic rings. 1 However, it is preferable that the cyclic group has both a ring (e.g., an aromatic ring) and a chain-like structure (e.g., a linear structure, ether oxygen, thioether sulfur), and specific examples include 1,3-phenylenebisalkylene group, 1,4-phenylenebisalkylene group, diphenyletherdiyl group, diphenylthioetherdiyl group, etc. 1 The number of carbon atoms may be 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more, and may also be 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, or 3 or less.

[0199] In amine-modified example 1, p is an integer between 0 and 2 (inclusive) independently in each occurrence, q is an integer between 0 and 2 (inclusive) independently in each occurrence, and p+q is each N(-XZ n ) p (New H) q In this case, it is 2. Preferably, p may be 1 or greater in each occurrence independently, for example, 2.

[0200] In amine-modified example 1, r is independently 0 or 1 in each occurrence, s is independently 0 or 1 in each occurrence, and r+s is each N(-XZ n ) r (New H) s In this case, it is 1. Preferably, p may be 1 or greater in each occurrence independently, for example, 2.

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

[0202] In amine-modified example 1, t is an integer between 0 and 10. t may be 0 or greater, 1 or greater, 2 or greater, 4 or greater, or 6 or greater, preferably 0 or greater or 2 or greater, and t may also be 8 or less, 6 or less, 4 or less, or 3 or less.

[0203] (Amine-modified example 2) Examples of other amine-modified compounds include the following formula: N(-XZ n ) p (New H) q -L 2 (-XZ n ) u [In the formula, X is, independently in each occurrence, a direct bond or a 1+n valence base. Z is a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have substituents, independently in each instance. L 2 This is a 1+u valent aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms, which may be cleaved by oxygen atoms and / or sulfur atoms. n is an integer between 1 and 3, independently of each occurrence. p is an integer between 0 and 2, q is an integer between 0 and 2, p+q is 2, u is an integer between 1 and 3, The sum of p and u is 1 or greater. A compound represented by (Amine Modified Compound Example 2) is an example.

[0204] In Amine Modification Example 2, the details of X, Z, and n are as described above.

[0205] In amine-modified example 2, L 2 L is a 1+u valent aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms, which may be cleaved by oxygen atoms and / or sulfur atoms, and may be a cyclic, branched, or linear hydrocarbon group, preferably a linear hydrocarbon group or an aromatic hydrocarbon. 2 As an example, the hydrocarbon group described above in the explanation of the [amine skeleton] may be used, and the hydrocarbon group may be divided by an oxygen atom and / or a sulfur atom, or it may consist only of a carbon atom, a nitrogen atom, and a hydrogen atom. 2 This may be, for example, a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1-2 hydrocarbon aromatic rings. 2 However, it is preferable that the cyclic group has both a ring (e.g., an aromatic ring) and a chain-like structure (e.g., a linear structure, ether oxygen, thioether sulfur), and specific examples include 1,3-phenylenebisalkylene group, 1,4-phenylenebisalkylene group, diphenyletherdiyl group, diphenylthioetherdiyl group, etc. 2 The number of carbon atoms may be 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more, and may also be 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, or 3 or less.

[0206] In amine-modified example 2, p is an integer between 0 and 2, q is an integer between 0 and 2, and p+q is 2. Preferably, p may be 1 or greater, for example, 2.

[0207] In amine-modified example 2, u is an integer between 1 and 3. u is 1, 2, or 3, for example, 2 or 3.

[0208] In amine-modified example 2, the sum of p and u is 1 or more, meaning that amine-modified example 2 has one or more -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 also be 5 or less, 4 or less, 3 or less, or 2 or less.

[0209] (Specific example) A specific example of an amine-modified compound is the compound represented by the following formula. For details regarding X, Z, and n in the following formula, please refer to the explanation above.

[0210] JPEG0007897514000003.jpg2830

[0211] JPEG0007897514000004.jpg2347

[0212] JPEG0007897514000005.jpg2635

[0213] JPEG0007897514000006.jpg1837

[0214] JPEG0007897514000007.jpg1547

[0215] JPEG0007897514000008.jpg1746

[0216] JPEG0007897514000009.jpg1553

[0217] Amine-modified compounds may be synthetic waxes derived from animal or vegetable oils. Synthetic waxes may be obtained by condensing fatty acids derived from animal or vegetable oils with aliphatic or aromatic amines. Examples of synthetic waxes include fatty acid amide compounds such as hydroxy fatty acid amides, palmitic acid amides, octadecanoic acid amides, stearic acid amides, arachidinic acid amides, behenic acid amides, lignoceric acid amides, oleic acid amides, linoleic acid amides, α-linolenic acid amides, γ-linolenic acid amides, arachidonic acid amides, eicosapentaenoic acid amides, and docosahexaenoic acid amides.

[0218] [Method for producing amine-modified compounds] Methods for producing amine-modified compounds are not limited to the above, but include methods of synthesis by reacting various amines (starting amines) with a Z-group-containing carboxylic acid, optionally in the presence of a coupling agent, and methods of synthesis by reacting various amines with Z-group-containing carboxylic acid acid chlorides, acid anhydrides, isocyanates, etc. The coupling agent may be any known coupling agent, such as DCC, EDCI, CDI, BOP, COMU, DMT-MM, DPPA, Py-Bop, etc.

[0219] (Amine (raw material amine)) Examples of amines (starter amines) that are precursors to the amine skeleton include alkylamines such as methylamine, ethylamine, propylamine, butylamine, and dibutylamine; alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, pentanediamine, hexamethylenediamine, cyclohexanediamine, and methylenebiscyclohexylamine; diethylenetriamine, triethylenetetramine, tris(2-aminoethyl)amine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripylenetetramine, tris(2-aminopropyl)amine, tetrapropylenepentamine, pentapropylenehexamine, iminobispropylamine, dibutylentriamine, bis(2-aminoethoxy)ethane, bis(2-aminoethyl) ether, bis[2-(2-aminoethoxy)ethyl] ether, and bis[2-(3-aminoprotoxy)ethyl] Polyalkylene polyamines such as ether, spermine, and spermidine; oxygen or sulfur-containing aliphatic amines such as 1-aminopropanediol, 2-amino-1,3-propanediol, 3-amino-1,2-propanediol, polyoxypropylenediamine, and polyoxyethylenediamine; aromatic monoamines such as aniline, 1- or 2-naphthylamine, 1-, 2- or 9-aminoanthracene, 9-aminophenanthracene, and 2-, 3- or 4-aminobiphenyl; monocyclic aromatic polyamines such as o-, m- or p-phenylenediamine, o-, m- or p-xylylenediamine, diaminotoluene, and 2,3-, 2,4- or 2,5-tolylenediamine;Diaminobiphenyl, bisaminophenoxyphenylpropane, diaminodiphenyl ether, diaminodiphenyl sulfide, diaminodiphenyl sulfone, diaminobenzophenone, diaminodiphenylmethane, diaminophenylpropane, diaminophenylhexafluoropropane, diaminophenylphenylethane, bisaminophenoxybenzene, bisaminobenzoylbenzene, bisaminodimethylbenzylbenzene, aminophenoxybiphenyl, aminophenoxyphenyl ketone, bisaminoditrifluoromethylbenzylbenzene, aminophenoxyphenyl sulfone, aminophenoxyphenyl ether, aminophenoxyphenylpropane, bis(aminophenoxybenzoyl)benzene, bis(aminophenoxy-α,α-dimethylbenzyl)benzene, bis[(aminoaryloxy)benzoyl]diphenyl ether, bis(amino-α,α-dimethylbenzylphenoxy)benzophenone, aminophenoxyphenyl sulfide, bis[amino-α, α-dimethylbenzylphenoxy]diphenyl sulfone, 4,4'-bis[aminophenoxyphenoxy]diphenyl sulfone, diaminodiaryloxybenzophenone, Polycyclic aromatic polyamines such as diaminoaryloxybenzophenone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diaminotriphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-methylenebisaniline, 4,4'-oxydianiline, 1,3-bis(4-aminophenoxy)benzene, 4,4'-diaminodiphenyl ether, and 4,4'-bis(aminophenyl)amine; oxygen or sulfur-containing polycyclic aromatic polyamines such as 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 3,4'-diaminodiphenyl ether, and 4,4'-diaminodiphenyl sulfide;Examples include hydroxyl group-containing polyamines such as 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, and di-2-hydroxypropylethylenediamine. The polyamine may also be obtained by polymerizing polymerizable compounds such as allylamine.

[0220] [Composition of liquid-repellent compounds] The liquid-repellent compound may use either the polyol-modified compound alone or the amine-modified compound, or a combination of both. The amount of the polyol-modified compound may be 10% or more by weight, 20% or more by weight, 30% or more by weight, 40% or more by weight, 50% or more by weight, 60% or more by weight, 70% or more by weight, 80% or more by weight, or 90% or more by weight relative to the total of the polyol-modified compound and the amine-modified compound, and may also be 95% or less by weight, 85% or less by weight, 75% or less by weight, 65% or less by weight, 55% or less by weight, 45% or less by weight, 35% or less by weight, 25% or less by weight, 15% or less by weight, or 5% or less by weight.

[0221] [Amount of liquid-repellent compound] The amount of the liquid-repellent compound may be 0.01% or more by weight, 0.5% or more by weight, 1% or more by weight, 3% or more by weight, 5% or more by weight, 10% or more by weight, 20% or more by weight, or 30% or more by weight in the repellent, and may also be 60% or less by weight, 50% or less by weight, 40% or less by weight, 30% or less by weight, 20% or less by weight, 10% or less by weight, 5% or less by weight, or 3% or less by weight.

[0222] [Dispersant] The repellent of this disclosure preferably includes a dispersant (e.g., a cationic dispersant).

[0223] The dispersant may be at least one selected from organic dispersants and inorganic dispersants. The dispersant may be at least one selected from anionic dispersants, nonionic dispersants, cationic dispersants, amphoteric dispersants, and inorganic dispersants.

[0224] The dispersant preferably contains a cationic dispersant. The dispersant may be a cationic dispersant alone, or it may be used in combination with other dispersants. Examples of dispersant combinations 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 so on, with a preferred combination being a cationic dispersant and a nonionic dispersant. The repellent does not have to contain dispersants other than cationic dispersants, such as anionic dispersants and / or nonionic dispersants (e.g., anionic dispersants). The dispersant may contain dispersants other than fatty acid esters having an HLB value of 7 or higher. For example, the dispersant may contain a fatty acid ester-based dispersant having an HLB value of less than 7, or it may contain dispersants other than fatty acid esters.

[0225] The dispersant may be either an organic dispersant or an inorganic dispersant, or a combination of both.

[0226] Organic dispersants may be used as dispersants. Organic dispersants can be classified into nonionic dispersants, anionic dispersants, cationic dispersants, and amphoteric dispersants, and the term "organic dispersant" may refer to surfactants.

[0227] The dispersant may be non-fluorinated.

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

[0229] The nonionic dispersant may be of low molecular weight or high molecular weight. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 100000 or less, 10000 or less, 7500 or less, 5000 or less, 25000 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] Examples of ethers are compounds having an oxyalkylene group (preferably a polyoxyethylene group).

[0232] Examples of esters are esters of alcohols and fatty acids. Examples of alcohols are 1-30 valencies (especially 2-10 valencies) with 1-50 carbon atoms (especially 10-30 carbon atoms) (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids with 2-50 carbon atoms, especially 5-30 carbon atoms.

[0233] Examples of ester ethers are compounds formed by adding an alkylene oxide (especially ethylene oxide) to an ester of an alcohol and a fatty acid. Examples of alcohols are 1-30 valencies (especially 2-10 valencies) with 1-50 carbon atoms (especially 3-30 carbon atoms) (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids with 2-50 carbon atoms, especially 5-30 carbon atoms.

[0234] Examples of alkanolamides are formed from fatty acids and alkanolamines. Alkanolamides may be monoalkanolamides or dialkanolaminos. Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. Alkanolamines may be alkanols having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0235] The polyol may be a divalent to pentavalent alcohol with 10 to 30 carbon atoms. The amine oxide may be an oxide of an amine (a secondary amine or preferably a tertiary amine) (for example, having 5 to 50 carbon atoms).

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

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

[0239] The nonionic dispersant is, formula: R 1 O-(CH2CH2O) p -(R 2 O) q -R 3 [In the formula, R 1This is an alkyl group having 1 to 22 carbon atoms, or an alkenyl group or acyl group having 2 to 22 carbon atoms. R 2 Each of these is independently identical or distinct, an alkylene group having 3 or more carbon atoms (e.g., 3 to 10). R 3 These are a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms. p is a number greater than or equal to 2. q is a number greater than or equal to 1, or 0. It may be a compound represented by [the formula shown].

[0240] R 1 The carbon atoms have 8 to 20 carbon atoms, and are more preferably 10 to 18 carbon atoms. 1 Preferred specific examples include the octyl group, nonyl group, trimethylnonyl group, lauryl group, tridecyl group, oleyl group, and stearyl group. R 2 Examples include the propylene group and the butylene group. In nonionic dispersants, p may be a number greater than or equal to 3 (e.g., 5 to 200). q may be a number greater than or equal to 2 (e.g., 5 to 200). That is, -(R 2 O) q - may form a polyoxyalkylene chain. The nonionic dispersant may be a polyoxyethylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) in the center. Examples of hydrophobic oxyalkylene chains include oxypropylene chains, oxybutylene chains, and styrene chains, but oxypropylene chains are preferred among these.

[0241] Specific examples of nonionic dispersants include ethylene oxide and hexylphenol, isooctatylphenol, hexadecanol, oleic acid, and alkanes (C 12 -C 16 ) Thiol, sorbitan monofatty acid (C7-C 19 ) or alkyl(C 12 -C 18This includes condensation products with 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 polyoxyethylene blocks can be 5 to 80% by weight, for example, 30 to 75% by weight, and especially 40 to 70% by weight, relative to the molecular weight of the nonionic dispersant (copolymer). The average molecular weight of nonionic dispersants is generally 300 to 5,000, for example, 500 to 3,000. The nonionic dispersant may be a single compound or a mixture of two or more compounds. The nonionic dispersant may be a mixture of compounds with an HLB (hydrophilic-hydrophobic balance) of less than 15 (especially 5 or less) and compounds with an HLB of 15 or more. Specifically, it is preferable to select from polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene, polyoxypropylene with an HLB of 1 to 18, or from sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene glycerin fatty acid esters, and polyoxyethylene sorbitan fatty acid esters with an HLB of less than 7.

[0243] [Cationic dispersant] The dispersant may contain a cationic dispersant. The cationic dispersant may be a cationic surfactant. The cationic dispersant may be a compound that does not have an amide group.

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

[0245] Cationic dispersants may be aliphatic or aromatic, such as ammonium salts (e.g., quaternary ammonium salts). Cationic dispersants may also be oxyethylene-added ammonium salts. Specifically, examples include amine salt type dispersants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazoline; quaternary ammonium salt type dispersants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, and benzethonium chloride; and polymeric 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. It may be a compound represented by R. 21 , R 22 , R 23 and -R 24Specific examples of X are alkyl groups (e.g., methyl group, butyl group, stearyl group, palmityl group). Specific examples of X are halogens (e.g., chlorine) and acids (e.g., hydrochloric acid, acetic acid). The cationic dispersant may be a monoalkyltrimethylammonium salt (alkyl group with 4 to 40 carbon atoms).

[0247] Specifically, low-molecular-weight cationic dispersants have the formula: R 1 p -N + R 2 q X - [In the formula, R 1 is C12 or higher (for example, C 12 ~C 50 ) is a linear and / or branched aliphatic (saturated and / or unsaturated) group, R 2 The elements are H or C1-C4 alkyl groups, benzyl groups, and polyoxyethylene groups (number of oxyethylene groups, for example, 1 (particularly 2, especially 3) to 50) (CH3 and C2H5 are particularly preferred). X is a halogen atom (e.g., chlorine), or a C1-C4 fatty acid salt, or a C1-C4 sulfonate. p is either 1 or 2, q is either 2 or 3, and p + q = 4. It may be an ammonium salt represented by R. 1 The number of carbon atoms can be 12 to 50, for example, 12 to 30.

[0248] Low molecular weight cationic dispersants may include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydropolyoxyethylene)ammonium chloride, benzyldodecyldi(hydropolyoxyethylene)ammonium chloride, N-[2-(diethylamino)ethyl]oleamide hydrochloride, etc.

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

[0250] [Anionic dispersant] The dispersant may contain an anionic dispersant. The anionic dispersant may be an anionic surfactant. The dispersant does not have to contain an anionic dispersant.

[0251] The anionic dispersant may be of low molecular weight or high molecular weight. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 100000 or less, 10000 or less, 7500 or less, 5000 or less, 25000 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-sulfone fatty acid salts, N-acyl amino acid type dispersants, phosphate mono or diester type dispersants, and sulfosuccinate esters.

[0253] [Amphoteric dispersant] The dispersant may contain an amphoteric dispersant. The amphoteric dispersant may be an amphoteric surfactant.

[0254] The amphoteric dispersant may be of low molecular weight or high molecular weight. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 100000 or less, 10000 or less, 7500 or less, 5000 or less, 25000 or less, 750 or less, or 250 or less.

[0255] Examples of amphoteric dispersants include alanines, imidazolinium betaines, amide betaines, and betaine acetate. Specifically, these include lauryl betaine, stearyl betaine, laurylcarboxymethylhydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, and fatty acid amidopropyldimethylaminoacetic acid betaine.

[0256] [Inorganic dispersants] The dispersant may contain an inorganic dispersant.

[0257] The average primary particle size of the inorganic dispersant may be 5 nm or larger, 30 nm or larger, 100 nm or larger, 1 μm or larger, 10 μm or larger, or 25 μm or larger, and may also be 100 μm or smaller, 50 μm or smaller, 10 μm or smaller, 1 μm or smaller, 500 nm or smaller, or 300 nm or smaller. The average primary particle size can be measured, for example, by observation with a microscope (scanning electron microscope or transmission electron microscope). The inorganic dispersant may also be hydrophilic particles.

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

[0260] [Liquid media] The repellent in this disclosure may include a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The repellent may be a dispersion or a solution. The repellent in this disclosure is water-dispersible and may contain at least water.

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

[0262] [Amount of liquid medium] The amount of liquid medium may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, or 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, or 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, per 1 part by weight of the liquid-repellent compound.

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

[0264] The amount of organic solvent may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, or 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, per 1 part by weight of the liquid-repellent compound.

[0265] 〔silicone〕 The repellent agent in this disclosure may include silicone (polyorganosiloxane). By including silicone, it is possible to achieve good liquid repellency in addition to good texture and durability.

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

[0267] The weight-average molecular weight of the silicone may be 1000 or more, 10000 or more, or 50000 or more, and may also be 500000 or less, 2500000 or less, 100000 or less, or 50000 or less.

[0268] [Amount of silicone] The amount of silicone may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, per 100 parts by weight of the liquid-repellent compound, or 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0269] 〔wax〕 The repellent in this disclosure may include wax. Including wax can effectively impart 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 plant waxes, and mineral waxes. Paraffin wax is preferred. Specific examples of compounds that constitute the wax include n-alkanes (e.g., tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentacontane, hexatriacontane) and n-alkenes (e.g., 1-eicosene, 1-docosene, 1-tricocene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentacontane, hexatriacontane). The number of carbon atoms in the compounds that constitute the wax is preferably 20 to 60, for example, 25 to 45. The molecular weight of the wax may be 200 to 2000, for example, 250 to 1500 or 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, and 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 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, per 100 parts by weight of the liquid-repellent compound, and may also be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0273] [Organic acid] The repellent agent of this disclosure may contain an organic acid. Any known organic acid can be used. Preferred organic acids include carboxylic acids, sulfonic acids, sulfinic acids, etc., with carboxylic acids being particularly preferred. Examples of carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid, etc., with formic acid or acetic acid being particularly preferred. In this disclosure, one organic acid may be used, or two or more may be used in combination. For example, formic acid and acetic acid may be used in combination.

[0274] [Amount of organic acids] The amount of organic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more per 100 parts by weight of the liquid-repellent compound, or 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less. The amount of organic acid may be adjusted so that the pH of the repellent is 3 to 10, for example 5 to 9, particularly 6 to 8. The repellent may be acidic (pH 7 or less, for example 6 or less).

[0275] [Hardening agent] The repellent agent of this disclosure may contain a curing agent (an active hydrogen-reactive compound or an active hydrogen-containing compound).

[0276] The curing agent (crosslinking agent) in a 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 present in the liquid-repellent compound. Examples of active hydrogen-reactive compounds include isocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds, and hydrazide compounds. Examples of active hydrogen-containing compounds include 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 contain an isocyanate compound. The isocyanate compound may be a polyisocyanate compound. A polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound acts as a crosslinking agent. Examples of polyisocyanate compounds include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic aliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates. The isocyanate compound may be a blocked isocyanate compound (for example, a blocked polyisocyanate compound). A blocked isocyanate compound is a compound in which the isocyanate groups of an isocyanate compound are masked with a blocking agent to suppress the reaction.

[0278] Examples of aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, and 2,6-diiso These include aliphatic diisocyanates such as cyanatomethyl caproate, and aliphatic triisocyanates such as lysine ester triisocyanate, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, and 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane. These may be used alone or in combination of two or more.

[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 individually or in combination of two or more.

[0280] Examples of aromatic aliphatic polyisocyanates include aromatic aliphatic diisocyanates and aromatic aliphatic triisocyanates. Specific examples of aromatic aliphatic polyisocyanates include 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethylxylylene diisocyanate) or mixtures thereof, and 1,3,5-triisocyanatomethylbenzene. These may be used individually or in combination of two or more.

[0281] Examples of aromatic polyisocyanates include aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates include m-phenylenediisocyanate, p-phenylenediisocyanate, 4,4'-diphenyldiisocyanate, 1,5-naphthalenediisocyanate, 2,4'- or 4,4'-diphenylmethanediisocyanate or mixtures thereof, 2,4- or 2,6-tolylenediisocyanate or mixtures thereof, triphenylmethane-4,4',4''-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate. These may be used individually or in combination of two or more.

[0282] Examples of polyisocyanate derivatives include various derivatives of the polyisocyanate compounds described above, such as dimers, trimers, biuretes, allophanates, carbodiimides, uretodiones, uretoimines, isocyanurates, and iminooxadiazinediones. These may be used individually or in combination of two or more.

[0283] These polyisocyanates can be used individually or in combination of two or more types. It is preferable to use a blocked polyisocyanate compound (blocked isocyanate), which is a compound in which the isocyanate group of a polyisocyanate compound is blocked with a blocking agent, as the polyisocyanate compound. It is preferable to use a blocked polyisocyanate compound because it is relatively stable in solution and can be used in the same solution as the repellent agent.

[0284] Blocking agents sequester free isocyanate groups. Blocked polyisocyanate compounds can be easily reacted with hydroxyl groups by heating them to, for example, 100°C or higher, such as 130°C or higher, which regenerates the isocyanate groups. Examples of blocking agents include phenolic compounds, lactam compounds, aliphatic alcohol compounds, and oxime compounds. Polyisocyanate compounds can be used alone or in combination of two or more.

[0285] Epoxy compounds are compounds that have an epoxy group. Examples of epoxy compounds include epoxy compounds having a polyoxyalkylene group, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether. A chloromethyl group-containing compound is a compound that has a chloromethyl group. Examples of chloromethyl group-containing compounds include chloromethyl polystyrene. Carboxyl group-containing compounds are compounds that have a carboxyl group. Examples of carboxyl group-containing compounds include (poly)acrylic acid and (poly)methacrylic acid.

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

[0287] [Amount of hardener] The amount of curing agent may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, per 100 parts by weight of the liquid-repellent compound, or 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0288] [Other ingredients] The repellent agent may contain other components besides those listed above. Examples of other components include polysaccharides, paper strength enhancers, flocculants, yield enhancers, coagulants, binder resins, anti-slip agents, sizing agents, paper strength enhancers, fillers, antistatic agents, preservatives, UV absorbers, antibacterial agents, deodorizers, fragrances, etc. These may be used individually or in combination of two or more. In addition to the above-mentioned components, other components include other water-repellent and / or oil-repellent agents, dispersants, texture modifiers, softeners, flame retardants, paint fixatives, wrinkle inhibitors, drying speed modifiers, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, insect repellents, defoamers, shrinkage inhibitors, wrinkle inhibitors, shape-retaining agents, drape-retaining agents, ironing improvers, whitening agents, whitening agents, fabric softening clay, color transfer inhibitors such as polyvinylpyrrolidone, polymer dispersants, stain removers, scum dispersants, fluorescent whitening agents such as 4,4-bis(2-sulfostyryl)biphenyldisodium (Chinopearl CBS-X, manufactured by Ciba Specialty Chemicals), dye fixatives, and color-fading inhibitors such as 1,4-bis(3-aminopropyl)piperazine. In addition, enzymes such as cellulase, amylase, protease, lipase, and keratinase can be used as stain removers and fiber surface modifiers; silk protein powder can be used as a foam inhibitor and to impart the texture and functionality of silk, such as moisture absorption and release properties; surface modifiers or emulsified dispersions thereof (e.g., K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical), hydrolyzed silk liquid (Jomo), Silkgen G Solubble S (Ichimaru Falcos)); and anti-fouling agents (e.g., nonionic polymer compounds consisting of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units (e.g., FR627 manufactured by Go-o Chemical Industry), SRC-1 manufactured by Clariant Japan, etc.). These may be used individually or in combination of two or more.

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

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

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

[0292] [Antistatic agent] Examples of antistatic agents include cationic antistatic agents having cationic functional groups such as quaternary ammonium salts, pyridinium salts, and primary, secondary, and tertiary amino groups; anionic antistatic agents having anionic functional groups such as sulfonates, sulfate esters, phosphonates, and phosphate esters; amphoteric antistatic agents such as alkyl betaines and their derivatives, imidazolines and their derivatives, alanine and its derivatives; and nonionic antistatic agents such as amino alcohols and their derivatives, glycerin and its derivatives, polyethylene glycol and its derivatives. These may also be ion-conductive polymers obtained by polymerizing or copolymerizing monomers having cationic, anionic, or amphoteric ion-conductive groups. These may be used individually or in combination of two or more.

[0293] [Preservatives] Preservatives are primarily used to enhance preservative and bactericidal properties and maintain preservation during long-term storage. Examples of preservatives include isothiazolone-type organosulfur compounds, benzisothiazolone-type organosulfur compounds, benzoic acids, and 2-bromo-2-nitro-1,3-propanediol.

[0294] [UV absorber] UV absorbers are chemicals that have the effect of protecting against ultraviolet rays. They absorb ultraviolet rays and convert them into infrared rays, visible light, etc., and release them. Examples of UV absorbers include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole compounds, and 4-t-butyl-4'-methoxybenzoylmethane.

[0295] [Antibacterial agent] Antibacterial agents are components that suppress the growth of bacteria on fibers and also suppress the generation of unpleasant odors derived from microbial decomposition products. Examples of antibacterial agents include cationic disinfectants such as quaternary ammonium salts, bis-(2-pyridylthio-1-oxide)zinc, polyhexamethylene biguanidine hydrochloride, 8-oxyquinoline, and polylysine.

[0296] [Deodorizer] Examples of deodorizers include cluster dextrin, methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamidopropyldimethylamine oxide, and aminocarboxylic acid metal complexes (such as the zinc complex of trisodium methylglycinediacetate described in International Publication No. 2012 / 090580).

[0297] [Amount of other ingredients] The individual or total amounts of the other components may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, per 100 parts by weight of the liquid-repellent compound, and may also be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0298] <Method for manufacturing processed textile or paper products> The method for manufacturing a product treated with a repellent in this disclosure includes a processing step of treating a substrate with the repellent described above.

[0299] "Treatment" means applying the repellent to the substrate by dipping, spraying, coating, etc. Through treatment, the liquid-repellent compound, which is the active ingredient of the repellent, adheres to the interior and / or surface of the substrate. Here, adhesion may be physical or chemical, and for example, the liquid-repellent compound may be physically or chemically modified (by reaction) the hydroxyl groups present in the substrate (fiber, paper, glass, etc.).

[0300] [Base material] The substrates treated with the repellent in this disclosure are not limited, but are preferably textile products or paper products, particularly paper products.

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

[0302] Examples of base materials for textile products include natural animal and plant fibers such as cotton, linen, wool, and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers such as rayon and acetate; inorganic fibers such as glass fibers, carbon fibers, and asbestos fibers; or blends thereof. Textile products include woven fabrics, knitted fabrics, and nonwoven fabrics; fabrics in the form of clothing (e.g., water-repellent clothing, e.g., raincoats) and carpets; however, fibers, yarns, and intermediate textile products (e.g., slivers or rovings) in their pre-fabric state may also be treated.

[0303] Examples of base materials for paper products include paper made from bleached or unbleached chemical pulps such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulps such as crushed wood pulp, mechanical pulp or thermomechanical pulp, recycled paper pulp such as recycled newspaper, recycled magazine, recycled corrugated cardboard or deinked paper, as well as containers and molded bodies made of paper. Specific examples of paper products include food packaging materials, food containers, gypsum board base paper, coated base paper, medium-grade paper, general liners and cores, neutral pure white roll paper, neutral liners, rust-preventive liners and metal interleaving paper, kraft paper, neutral printing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper, molded paper (molded containers), etc. Preferred examples include food packaging materials and food containers.

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

[0305] When the substrate is glass, the manufactured glass product may be an optical component. A layer (or film), such as a hard coat layer or an anti-reflective layer, may be formed on the surface (outermost layer) of the glass substrate. Either a single-layer anti-reflective layer or a multi-layer anti-reflective layer may be used for the anti-reflective layer. Examples of inorganic materials that can be used for the anti-reflective layer include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, CeO2, MgO, Y2O3, SnO2, MgF2, and WO3. These inorganic materials may be used individually or in combination of two or more (for example, as a mixture). When a multi-layer anti-reflective layer is used, it is preferable to use SiO2 and / or SiO for the outermost layer. When the article to be manufactured is an optical glass component for a touch panel, a thin film using a transparent electrode, such as indium tin oxide (ITO) or indium zinc oxide, may be present on part of the surface of the substrate (glass). Furthermore, the substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomizing film layer, a hard coating film layer, a polarizing film, a phase difference film, and a liquid crystal display module, depending on its specific specifications.

[0306] [Processing method] The repellent agent of this disclosure can be applied to a substrate by conventionally known methods as a treatment agent (particularly a surface treatment agent). The treatment method may involve diluting the repellent agent of this disclosure by dispersing it in an organic solvent or water as needed, and then applying it to the interior and / or surface of the substrate by known methods such as immersion coating, spray coating, or foam coating, followed by drying. After drying, a product with the solid components of the repellent agent attached is obtained. Furthermore, if necessary, it may be applied together with a suitable crosslinking agent and curing may be performed. The repellent agent of this disclosure may also be used in combination with various additives as needed, such as water-repellent and / or oil-repellent agents, anti-slip agents, antistatic agents, texture modifiers, softeners, antibacterial agents, flame retardants, paint fixatives, anti-wrinkle agents, drying rate modifiers, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, insecticides, and defoaming agents. Examples of various additives may be the same as those described under "other components" in the above description. The concentration of the repellent in the treatment agent that comes into contact with the substrate may be changed as appropriate depending on the application, but it 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 known method for treating the substrate with a liquid. The substrate may be immersed in the repellent, or the solution may be applied to 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 this disclosure, good performance can be obtained even with low-temperature heating (e.g., 100°C to 140°C). In this 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 repellent may be coated onto the paper, or the solution may be applied to or sprayed onto the paper, or it may be mixed with the pulp slurry before papermaking. The treatment may be an external or internal addition. Alternatively, the repellent may be applied to the textile product by a cleaning method, for example, by washing or dry cleaning.

[0308] [Disposal of paper products] Examples of paper substrates include paper, paper containers, and molded paper products (e.g., pulp molds). The liquid-repellent compounds of this disclosure adhere well to paper substrates.

[0309] Paper can be manufactured using conventionally known papermaking methods. Either an internal additive method, in which a repellent agent is added to the pulp slurry before papermaking, or an external additive method, in which a repellent agent is applied to the paper after papermaking, can be used.

[0310] The size press for external additive processing can also be classified as follows, depending on the application method. One coating method is the so-called pound-type two-roll sizing press, in which a coating liquid (sizing liquid) is supplied to a nip formed by passing paper between two rubber rolls, creating a coating liquid reservoir called a pound, and the sizing liquid is applied to both sides of the paper by passing it through this reservoir. Other coating methods include the gate-roll type and the rod-metering sizing press, which apply the sizing liquid by surface transfer. In the pound-type two-roll sizing press, the sizing liquid easily penetrates into the interior of the paper, while in the surface transfer type, the sizing liquid components tend to remain on the surface of the paper. Compared to the pound-type two-roll sizing press, the surface transfer type allows the coating layer to remain on the surface of the paper more easily, and the coating layer formed on the surface is greater than that of the pound-type two-roll sizing press. In this disclosure, performance can be imparted to the paper even when the former pound-type two-roll sizing press is used. Paper treated in this way can exhibit excellent oil resistance and water resistance, etc., after simple drying at room temperature or high temperature, and optionally with heat treatment that can be performed at temperatures up to 300°C, for example up to 200°C, particularly in the temperature range of 80°C to 180°C, depending on the properties of the paper.

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

[0312] This 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-preventive liners and metal laminates, kraft paper, and the like. 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, wood pulp, mechanical pulp or thermomechanical pulp, etc. Any type of recycled paper pulp can be used, including bleached or unbleached high-yield pulp, recycled newspaper, recycled magazine, recycled corrugated cardboard, or deinked recycled paper. Mixtures of the above pulp raw materials with synthetic fibers such as asbestos, polyamide, polyimide, polyester, polyolefin, and polyvinyl alcohol can also be used.

[0314] The water resistance of paper can be improved by adding a sizing agent. Examples of sizing agents 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 sizing agent may be 0.01 to 5% by weight relative to the pulp.

[0315] If necessary, the paper may contain additives used in papermaking, such as paper strength enhancers, flocculants, fixatives, yield improvers, dyes, fluorescent dyes, slime control agents, and defoamers, as commonly used papermaking agents, including starch, modified starch, carboxymethylcellulose, and polyamide polyamine-epichlorohydrin resin. Starch and modified starch are preferred. If necessary, a repellent agent can be applied to the paper using a size press, gate roll coater, bill blade coater, calender, etc., with starch, polyvinyl alcohol, dyes, coating colors, anti-slip agents, etc.

[0316] In external additions, the amount of liquid-repellent compound contained in the coating layer is 0.01 to 2.0 g / m². 2 Especially 0.1~1.0g / m 2 Preferably, the coating layer is formed of a repellent and starch and / or modified starch. The solid content of the paper repellent in the coating layer is 2 g / m². 2 The following is preferable: In the internal addition process, it is preferable to mix the repellent with the pulp such that the amount of 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 pulp used to form the paper.

[0317] In external application, oil resistance can also be imparted to paper by using a so-called pound-type two-roll size press process, in which the processing liquid is stored between the rolls and the base paper is passed through the processing liquid between the rolls at an arbitrary roll speed and nip pressure.

[0318] In external additive processing, the paper substrate may contain additives such as sizing agents, paper strength enhancers, flocculants, yield enhancers, or coagulants. The additives may be nonionic, cationic, anionic, or amphoteric. The ionic charge density of the additives is -10000 to 10000 μeq / g, preferably -4000 to 8000 μeq / g, and more preferably -1000 to 7000 μeq / g. Additives such as sizing agents, paper strength enhancers, flocculants, yield enhancers, or coagulants (solid content 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) relative to the pulp. In the case of a paper substrate containing cationic additives (e.g., sizing agents, paper strength enhancers, flocculants, yield enhancers, or coagulants), the repellent is preferably anionic.

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

[0320] [Pretreatment of textile products] Textile products may be pre-treated before being treated with the repellent of this disclosure. Pre-treating the textile products can impart excellent fastness to the textile products after treatment with the repellent.

[0321] Examples of pretreatments for textile products include cationization by reaction with reactive quaternary ammonium salts, anionization by sulfonation, carboxylation, phosphorylation, etc., acetylation, benzoylation, carboxymethylation, grafting, tannic acid treatment, and polymer coating after anionization.

[0322] The method for pre-treating textile products is not limited, but conventionally known methods can be used. The pre-treatment solution may be diluted by dispersing it in an organic solvent or water as needed, and then applied to the interior and / or surface of the textile product by known methods such as immersion coating, spray coating, or foam coating, followed by drying. The pH and temperature of the pre-treatment solution may be adjusted according to the desired degree of treatment. As an example of a method for pre-treating textile products, a method of pre-treating textile products with the above-mentioned treatment agent will be described in detail.

[0323] The pretreatment method for textile products involves applying -SO3M to the fibers. 1 (In the formula, M 1 (represents a monovalent cation) a monovalent group represented by -COOM 2 (In the formula, M 2 A monovalent group represented by (where is a monovalent cation), and -OP(O)(OX 1 )(OX 2 )(wherein, X 1 and X 2 The process may include a step of adding one or more functional groups (hereinafter sometimes referred to as "specific functional groups") selected from the group consisting of monovalent groups (each independently representing a hydrogen atom or an alkyl group having 1 to 22 carbon atoms).

[0324] M 1 Examples include H, K, Na, or ammonium ions which may have substituents. 2 Examples include H, K, Na, or ammonium ions which may have substituents. 1 or X 2 If it 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] Fibers containing the above-mentioned 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 above-mentioned specific functional group is attached to the fiber material. The attachment of the compound may be such that a portion of the compound and a portion of the fiber are chemically bonded, to the extent that a sufficient amount of the above-mentioned specific functional group remains. (ii) Prepare a fiber in which the above-mentioned specific functional group is directly introduced into the material constituting the fiber.

[0326] (i) For example, a functional group-containing fiber can be obtained by a functional group introduction step in which the fiber material is treated with a pretreatment solution containing one or more compounds having the above-mentioned specific functional group.

[0327] There are no particular restrictions on the material of the fiber material, and examples include natural fibers such as cotton, linen, silk, and wool; semi-synthetic fibers such as rayon and acetate; synthetic fibers such as polyamide (nylon, etc.), polyester, polyurethane, and polypropylene; and composite fibers and blended fibers thereof. The fiber material may take any form, such as fibers (tow, sliver, etc.), yarn, knitted fabrics (including interwoven fabrics), woven fabrics (including interwoven fabrics), and nonwoven fabrics.

[0328] In this embodiment, from the viewpoint of obtaining good water repellency in the resulting textile product, it is preferable to use a fiber material containing polyamide and polyester as a base material. In particular, it is preferable to use nylon such as nylon 6 and nylon 6,6, polyester such as polyethylene terephthalate (PET), polytrimethyl terephthalate, and polylactic acid, and mixed fibers containing these.

[0329] The above -SO3M 1 As a compound having this property, phenolic polymers can be used. Examples of such phenolic polymers include those containing at least one compound represented by the following general formula.

[0330] TIFF0007897514000010.tif4770 [In the formula, X 2 ha-SO3M 3 (In the formula, M 3 (where n represents a monovalent cation) or a group represented by the following general formula, where n is an integer between 20 and 3000.

[0331] TIFF0007897514000011.tif2758 [In the formula, M 4 This represents a monovalent cation.

[0332] The above M 3 Examples include H, K, Na, or ammonium ions which may have substituents.

[0333] The above M 4 Examples include H, K, Na, or ammonium ions which may have substituents.

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

[0335] The above-COOM 2 Examples of compounds having this property include polycarboxylic acid polymers.

[0336] As polycarboxylic acid polymers, for example, polymers synthesized by conventionally known radical polymerization methods using acrylic acid, methacrylic acid, maleic acid, etc. as monomers, or commercially available polymers can be used.

[0337] One method for producing polycarboxylic acid polymers is to add a radical polymerization initiator to an aqueous solution of the monomer and / or its salt, and heat the reaction at 30 to 150°C for 2 to 5 hours. At this time, alcohols such as methanol, ethanol, isopropyl alcohol, or aqueous solvents such as acetone may be added to the aqueous solution of the monomer and / or its salt. Examples of radical polymerization initiators include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, redox polymerization initiators using combinations of persulfates and sodium bisulfite, hydrogen peroxide, and water-soluble azo 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 to adjust the degree of polymerization.

[0338] In radical polymerization, copolymerizable monomers can be used in addition to the monomers mentioned above. Examples of copolymerizable monomers include vinyl monomers such as ethylene, vinyl chloride, and vinyl acetate, as well as acrylamide, acrylates, and methacrylates. Acrylates and methacrylates are preferably those having a hydrocarbon group with 1 to 3 carbon atoms, which may have substituents such as hydroxyl groups. 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 individually or in combination of two or more.

[0339] The carboxyl groups in the polycarboxylic acid polymer may be free or neutralized by alkali metals or amine compounds. Examples of alkali metals include sodium, potassium, and lithium, while examples of amine compounds include ammonia, monoethanolamine, diethanolamine, and triethanolamine.

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

[0341] For polycarboxylic acid polymers, commercially available products such as "NeoCrystal 770" (manufactured by Nikka Chemical Co., Ltd., product name) and "Cellopol PC-300" (manufactured by Sanyo Chemical Industries, Ltd., product name) can be used.

[0342] The above - OP(O)(OX 1 )(OX 2 Examples of compounds having the following general formula include phosphate ester compounds. TIFF0007897514000012.tif3236[where, X 1 or X 2 This is synonymous with the above, X 3 This represents an alkyl group with 1 to 22 carbon atoms.

[0343] As the phosphate ester compounds mentioned above, phosphate monoesters, diesters, and triesters in which the alkyl ester portion has an alkyl group having 1 to 22 carbon atoms, as well as mixtures thereof, can be used.

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

[0345] For the phosphate ester compound, commercially available products such as "Phosphanol ML-200" (manufactured by Toho Chemical Industry Co., Ltd., trade name) can be used.

[0346] The pretreatment solution containing one or more compounds having the above-mentioned specific functional groups can, for example, be an aqueous solution of the compounds described above. The pretreatment solution may also contain acids, alkalis, surfactants, chelating agents, etc.

[0347] Methods for treating fibrous materials with the above-mentioned pretreatment solution include, for example, padding, immersion, spraying, and coating. For padding, for example, methods using padding equipment described on pages 396-397 of the Dictionary of Textile Dyeing and Processing (published in 1963 by Nikkan Kogyo Shimbun) and pages 256-260 of Color Dyeing Chemistry III (published in 1975 by Jikkyo Shuppan Co., Ltd.) can be used. For coating, for example, methods using coating machines described on pages 473-477 of the General Catalog of Dyeing and Finishing Equipment (published in 1981 by Senryo-sha) can be used. For immersion, for example, methods using batch-type dyeing machines described on pages 196-247 of the General Catalog of Dyeing and Finishing Equipment (published in 1981 by Senryo-sha) can be used, and liquid flow dyeing machines, air flow dyeing machines, drum dyeing machines, winch dyeing machines, washer dyeing machines, cheese dyeing machines, etc. can be used. Examples of spray treatments include air sprays that atomize the treatment solution using compressed air, and air sprays that use a hydraulic atomization system. The concentration of the treatment solution and the treatment conditions such as heat treatment after application can be adjusted as appropriate, taking into account the purpose, performance, and other conditions. If the pretreatment solution contains water, it is preferable to dry it to remove the water after it has been applied to the fiber material. There are no particular restrictions on the drying method, and either a dry heat method or a wet heat method may be used. There are no particular restrictions on the drying temperature, but for example, drying at room temperature to 200°C for 10 seconds to several days is sufficient. If necessary, after drying, heat treatment may be performed at a temperature of 100 to 180°C for about 10 seconds to 5 minutes.

[0348] Furthermore, if the fiber material is to be dyed, the pretreatment with the pretreatment solution may be performed before dyeing or in the same bath as the dyeing. However, if reducing soaping is performed, there is a risk that the compounds having the specific functional groups (e.g., phenolic polymer compounds, etc.) that have been adsorbed during the process may be removed. Therefore, it is preferable to perform the pretreatment after reducing soaping following dyeing.

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

[0350] In the functional group introduction step using the pretreatment solution, it is preferable to treat the material in such an amount that the amount of compound having the specified functional group attached is 1.0 to 7.0 parts by weight per 100 parts by weight of the fiber material. Within this range, a high level of both durable water repellency and texture can be achieved.

[0351] The pretreatment solution is preferably adjusted to a pH of 3-5. pH adjustment can be done using pH adjusting agents such as acetic acid or malic acid.

[0352] The pretreatment solution may also contain salt to effectively adsorb the compound having the above-mentioned specific functional group onto the fiber material through a salting-out effect. Examples of salts that can be used include sodium chloride. Examples include sodium carbonate, ammonium sulfate, and sodium sulfate.

[0353] In the functional group introduction step using the pretreatment solution, it is preferable to remove any compounds having the specified functional groups that have been excessively treated. One method of removal is washing with water. By performing sufficient removal, it is possible to suppress the inhibition of the development of water repellency in the subsequent water-repellent treatment, and in addition, the texture of the resulting textile product will be good. Furthermore, it is preferable to thoroughly dry the resulting functional group-containing fibers before contacting them with the above-mentioned treatment agent.

[0354] (ii) Examples of fibers in which the above-mentioned specific functional groups are directly introduced into the material constituting the fiber include cationic dyeable polyester (CD-PET).

[0355] From the viewpoint of obtaining good water repellency in the resulting textile product, the functional group-containing fibers preferably have a surface zeta potential of -100 to -0.1 mV, and more preferably -50 to -1 mV. The surface zeta potential of the fibers can be measured, for example, using the zeta potential / particle size measurement system ELSZ-1000ZS (manufactured by Otsuka Electronics Co., Ltd.).

[0356] Although embodiments have been described above, it should be understood that various modifications to the form and details are possible without departing from the spirit and scope of the claims. [Examples]

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

[0360] [Volume abundance ratio of particles larger than 1 μm] The frequency distribution (volume distribution) of water-dispersible repellents was measured using a laser diffraction / scattering device, and the proportion of particles larger than 1 μm was calculated from this volume. This value was then defined as the volume proportion of particles larger than 1 μm.

[0361] [Median diameter D50] The results were obtained by measuring the water-dispersible repellent using a laser diffraction / scattering device.

[0362] [HD contact angle] A 1.0% solids solution (or dispersion) of a liquid-repellent compound was spin-coated onto a silicon wafer at 2500 rpm for 25 seconds to obtain a spin-coated film. This film was then 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 drop was defined as the HD contact angle of the liquid-repellent compound.

[0363] [Water contact angle] A 1.0% solids solution (or dispersion) of a liquid-repellent compound was spin-coated onto a silicon wafer at 2500 rpm for 25 seconds to obtain a spin-coated film. This film was then 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 drop was taken as the water contact angle of the liquid-repellent compound.

[0364] [Preparation of pulp molds] An automatic mold molding machine was used to form the pulp mold. At the bottom, a mesh structure was placed on top of a metal pulp mold with numerous suction holes, and at the top, a metal tank was placed. A mixture of pulp slurry and a water-dispersible repellent was placed in the upper metal tank. From the side of the pulp mold opposite the mesh structure, the pulp-containing aqueous composition was sucked and dewatered through the pulp mold and mesh structure using a vacuum pump, and the solid components (pulp, etc.) contained in the pulp-containing aqueous composition were deposited on the mesh structure to obtain a pulp mold intermediate. Next, the obtained pulp mold intermediate was dried from above and below under a pressure of 0.05 to 5 MPa using a metal male-female mold heated to 60 to 250°C. This produced a pulp mold product molded into the shape of a container.

[0365] [65°C oil resistance test] The pulp molds were pre-treated by storing them for 12 hours under conditions of 23°C and 50% humidity. 100 ml of 65°C corn oil was poured into the pulp molds, and after standing at room temperature for 45 minutes, the corn oil was removed from the pulp molds, and the degree of penetration was evaluated. The following evaluation values ​​were set based on the degree of penetration. 5: No stains on the inside. 4: Stain on the inside. No stain on the reverse side. 3: There is a stain on the inside. There is a slight seepage on the reverse side. 2: There is a stain on the inside. The stain has seeped through to the back over less than 50% of the area. 1: There is a stain on the inside. The stain has seeped through to the back, covering more than 50% but less than 100% of the area. 0: Staining across the entire back side.

[0366] [Measurement of ion charge density] The anion demand of a 0.1 g / L aqueous solution of the sample is measured using a particle charge meter (BTG MUTEK PCD-04) with a 1 / 1000 N potassium polyvinylsulfonate solution, and the ionic charge density (cation charge density) is calculated from the following formula (1). Alternatively, the cation demand is measured similarly using a polydiallyldimethylammonium chloride solution instead of potassium polyvinylsulfonate, and the ionic charge density (anion charge density) is calculated from the following formula (1). Ion charge density (μeq / g) = A / B (1) A: Cation demand or anion demand (μeq / L) B: Sample solution concentration (g / L)

[0367] [Preparation of processed paper] A pulp slurry was prepared using wood pulp with a weight ratio of 60% by weight for LBKP (hardwood bleached kraft pulp) and 40% by weight for NBKP (softwood bleached kraft pulp), and a pulp filtration degree of 400 ml (Canadian Standard Freeness). A wet strength agent and a sizing agent were added to this pulp slurry and paper was produced using a wire screen paper machine with a paper density of 0.58 g / cm³. 3 Basis weight 45g / m² 2 This paper was used as the base paper for external processing (size press processing). The oil resistance (KIT value) of this base paper is 0, and the water resistance (Cobb value) is 52 g / m². 2 That was the case.

[0368] To this base paper, a treatment solution prepared by dissolving the compound in chloroform at a ratio of 14.9 mg / mL was applied using a Baker-type applicator with a gap set to 0 mil. This process was repeated three times, and the paper was dried at 140°C for 1 minute to produce the treated paper.

[0369] [Dispersion stability test] The aqueous dispersion repellent was left to stand at 25°C for 100 hours, and the state of the dispersion was checked. If the supernatant liquid became clear and the dispersion and aqueous medium separated, it was evaluated as '△: Poor', and if the dispersion and aqueous medium did not separate, it was evaluated as '〇: Good'. [Examples]

[0370] As a liquid-repellent compound, 2 g of decaglycerol dodecabehenyl ester (polyol modified, degree of polymerization 10, hydroxyl group substitution rate: 12 / 12*100 [100%], bio-based: 100%), 0.2 g of benzalkonium chloride, and 17.8 g of water were mixed to obtain precursor A of a water-dispersible repellent. Precursor A of the water-dispersible repellent was heated to 80°C and then cooled while stirring with a magnetic stirrer to obtain precursor B of the water-dispersible repellent. Precursor B of the water-dispersible repellent was treated three times in a high-pressure wet micronization apparatus under conditions of 245 MPa to obtain a water-dispersible repellent. The volume abundance of particles larger than 1 μm of the obtained water-dispersible repellent was 21%, and the median diameter D50 was 0.68 μm. The ionic charge density was +127 μeq / g. When the water-dispersible repellent was subjected to a dispersion stability test, it showed good dispersibility. A water-dispersible repellent was added to a pulp slurry with a concentration of 0.5 wt% so that it was at a ratio of 4 wt% relative to the pulp in terms of solid content, thereby preparing a pulp-containing water-dispersible repellent. The pulp-containing water-dispersible repellent was then fed into an automatic mold molding machine to produce pulp molds. The pulp mold was subjected to an oil resistance test at 65°C and scored 4 points. The results are shown in Table 1. [Examples]

[0371] As a liquid-repellent compound, 2 g of decaglycerol dodecabehenyl ester (polyol modified, degree of polymerization 10, hydroxyl group substitution rate: 12 / 12*100 [100%], bio-based: 100%), 0.1 g of benzalkonium chloride, and 17.9 g of water were mixed to obtain precursor A of a water-dispersible repellent. Precursor A of the water-dispersible repellent was heated to 80°C and then cooled while stirring with a magnetic stirrer to obtain precursor B of the water-dispersible repellent. Precursor B of the water-dispersible repellent was treated three times in a high-pressure wet micronization apparatus under conditions of 245 MPa to obtain a water-dispersible repellent. The volume abundance of particles larger than 1 μm of the obtained water-dispersible repellent was 25%, and the median diameter D50 was 0.52 μm. The ionic charge density was +41 μeq / g. When the water-dispersible repellent was subjected to a dispersion stability test, its dispersibility was good. A water-dispersible repellent was added to a pulp slurry with a concentration of 0.5 wt% so that it was at a ratio of 4 wt% relative to the pulp in terms of solid content, thereby preparing a pulp-containing water-dispersible repellent. The pulp-containing water-dispersible repellent was then fed into an automatic mold molding machine to produce pulp molds. The pulp mold was subjected to an oil resistance test at 65°C and scored 4 points. The results are shown in Table 1. [Examples]

[0372] As a liquid-repellent compound, 2 g of decaglycerol decabehenyl ester (polyol modified, degree of polymerization 10, hydroxyl group substitution rate: 7 / 12*100 [58%], bio-based: 100%), 0.2 g of benzalkonium chloride, and 17.8 g of water were mixed to obtain precursor A of a water-dispersible repellent. Precursor A of the water-dispersible repellent was heated to 80°C and then cooled while stirring with a magnetic stirrer to obtain precursor B of the water-dispersible repellent. Precursor B of the water-dispersible repellent was treated three times in a high-pressure wet micronization apparatus under conditions of 245 MPa to obtain a water-dispersible repellent. The volume abundance of particles larger than 1 μm of the obtained water-dispersible repellent was 18%, and the median diameter D50 was 0.78 μm. The ionic charge density was +118 μeq / g. When the water-dispersible repellent was subjected to a dispersion stability test, its dispersibility was good. A water-dispersible repellent was added to a pulp slurry with a concentration of 0.5 wt% so that it was at a ratio of 4 wt% relative to the pulp in terms of solid content, thereby preparing a pulp-containing water-dispersible repellent. The pulp-containing water-dispersible repellent was then fed into an automatic mold molding machine to produce pulp molds. The pulp mold was subjected to an oil resistance test at 65°C and scored 4 points. 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%], bio-based: 100%) based on JIS K 6953-1:2011. The biodegradability was 36% after 30 days of testing, 62% after 60 days, and 94% after 180 days. [Examples]

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

[0375] As a liquid-repellent compound, 2 g of decaglycerol dodecabehenyl ester (polyol modified, degree of polymerization 10, hydroxyl group substitution rate: 12 / 12*100 [100%], bio-based: 100%), 0.2 g of polyethylene oxide alkyl ether (alkyl carbon numbers 6-16, HLB: 7), and 17.8 g of water were mixed to obtain precursor A of a water-dispersible liquid repellent. Precursor A of the water-dispersible liquid repellent was heated to 80°C and then cooled while stirring with a magnetic stirrer to obtain precursor B of the water-dispersible liquid repellent. Precursor B of the water-dispersible liquid repellent was treated three times in a high-pressure wet micronization apparatus under conditions of 245 MPa to obtain a water-dispersible liquid repellent. The volume abundance of particles larger than 1 μm of the obtained water-dispersible liquid 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, it showed good dispersibility. A water-dispersible repellent was added to a pulp slurry with a concentration of 0.5 wt% so that it was at a ratio of 4 wt% relative to the pulp in terms of solid content, thereby preparing a pulp-containing water-dispersible repellent. The pulp-containing water-dispersible repellent was then fed into an automatic mold molding machine to produce pulp molds. The pulp mold was subjected to a 65°C oil resistance test 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, degree of polymerization 10, hydroxyl group substitution rate: 12 / 12*100 [100%], bio-based: 100%), 0.2 g of polyethylene oxide alkyl ether (alkyl carbon 6-16, HLB: 7), and 17.8 g of water were mixed to obtain precursor A of a water-dispersible repellent. This precursor A of the water-dispersible repellent was heated to 80°C, and then cooled while stirring with a magnetic stirrer to obtain a water-dispersible repellent. The volume abundance of particles larger than 1 μm of the obtained water-dispersible repellent was 82%, and the median diameter D50 was 57.1 μm. The ionic charge density was -80.9 μeq / g. When the water-dispersible repellent was subjected to a dispersion stability test, its dispersibility was poor. A water-dispersible repellent was added to a pulp slurry with a concentration of 0.5 wt% so that it was at a ratio of 4 wt% relative to the pulp in terms of solid content, thereby preparing a pulp-containing water-dispersible repellent. The pulp-containing water-dispersible repellent was then fed into an automatic mold molding machine to produce pulp molds. When the pulp mold was subjected to a 65°C oil resistance test, it scored 1 point. The results are shown in Table 1.

[0377] [Table 1] JPEG0007897514000013.jpg108164

[0378] By limiting the volume abundance of particles larger than 1 μm in the water-dispersible repellent to 30% or less, and by using a cationic dispersant, it is possible to achieve both dispersion stability and oil resistance at 65°C.

Claims

1. Liquid-repellent compounds that are polyol-modified, and Cationic dispersant A water-dispersible repellent containing, The volume abundance of particles larger than 1 μm, as measured by laser diffraction scattering, is 30% or less. A repellent agent having an ionic charge density of 1 μeq / g or more and 1000 μeq / g or less.

2. The repellent according to claim 1, wherein the volume median diameter measured by laser diffraction scattering is 1 μm or less.

3. The repellent according to claim 1, wherein the ion charge density is 10 μeq / g or more and 250 μeq / g or less.

4. The repellent according to claim 1, comprising a nonionic dispersant.

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

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

7. The aforementioned polyol modified product modifies one or more hydroxyl groups of the polyol with the following formula: -Y-Z ｎ [In the formula, Y is Y １ and Y ２ A 1+n valence base consisting of one or more selected from the group comprising, Y １ These are direct bonds: -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O) ２ -, -NR'-, -C(OR')R'-, and -C(OR')(-) ２ , -N(-) ２ (In the formula, R' is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms in each instance.) A group consisting of one or more selected from the group, Y ２ This group is composed of one or more selected from the group consisting of a di- to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have substituents, a di- to tetravalent hydrocarbon aromatic ring which may have substituents, and a di- to tetravalent heterocycle which may have substituents. Z is a monovalent hydrocarbon group having 1 to 40 carbon atoms, or a monovalent polysiloxane group, which may have substituents. n is an integer between 1 and 3 (inclusive). The repellent according to claim 1, which is a compound substituted with a group represented by .

8. Y of the polyol modified product -O-Y １１ - or -O-Y １１ -Y ２１ -Y １２ — [In the formula, each symbol is independent in each occurrence.] Y １１ However, the bonds are direct bonds, -C(=O)-, -C(=O)-NR'-, or -C(=S)-NR'-. Y ２１ However, it is a hydrocarbon group having 1 to 40 carbon atoms, which may have substituents. 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。] The repellent according to claim 7.

9. The repellent according to claim 1, wherein 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 hydroxyl group-containing compound polymers.

10. Polyols 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; The repellent according to claim 1, which is at least one selected from the group consisting of polyglycerin, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymer, hydroxypropyl (meth)acrylate polymer, and hydroxybutyl (meth)acrylate polymer.

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

12. The repellent according to claim 1, wherein the bio-based degree of the polyol-modified material is 20% or more.

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

14. The repellent according to claim 1, for use in textile products or paper products.

15. A product treated with the repellent according to any one of claims 1 to 14.

16. The product according to claim 15, which is a textile product or a paper product.

17. The product according to claim 15, wherein the paper is oil-resistant or water-resistant.

18. The product according to claim 15, which is a food packaging material or a food container.

19. A method for producing a treated product, comprising the step of treating a substrate with a repellent according to any one of claims 1 to 14.

20. The manufacturing method according to claim 19, wherein the above process is an internal additive process.

Images