Repellent

Abstract

To provide a novel repellent capable of imparting oil resistance to a base material (for example, fiber or paper).SOLUTION: A water dispersible repellent contains a modified form of polyol and a dispersant, the repellent satisfying one or more of (1) and (2). (1) Differential scanning calorimetry of the modified form of polyol or differential scanning calorimetry of a solid component obtained by removing the liquid medium from the repellent shows the temperature of the maximum endothermic peak in the temperature zone of 25°C-180°C is 55°C or more. (2) The modified form of polyol has at least four monovalent C20-40 hydrocarbon groups which may have substituents.SELECTED DRAWING: None

Description

[Technical field]

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

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

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

[0004] Patent Document 1 does not mention oil resistance.

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

[0006] The present disclosure includes the following aspects: [Section 1] A water-dispersible repellent comprising a modified polyol and a dispersant, A repellent that satisfies one or more of (1) and (2). (1) In a differential scanning calorimetry measurement of the polyol modified product, or in a differential scanning calorimetry measurement of a solid component obtained by removing the liquid medium from the repellent, the temperature of the maximum endothermic peak in the temperature range of 25°C to 180°C is 55°C or higher. (2) The modified polyol has four or more monovalent hydrocarbon groups having 20 to 40 carbon atoms, each of which may have a substituent. [Section 2] Item 2. The repellent according to item 1, wherein the polyol modified product has a maximum endothermic peak temperature of 55° C. or higher in a temperature range of 25° C. to 180° C. in differential scanning calorimetry. [Section 3] Item 3. The repellent according to item 1 or 2, wherein in differential scanning calorimetry of a solid component obtained by removing the liquid medium from the repellent, the temperature of a maximum endothermic peak in a temperature range of 25° C. to 180° C. is 55° C. or higher. [Section 4] The peak intensity A of the maximum peak at a measurement temperature of 25°C in the 2θ range of 15° to 30° measured by variable temperature X-ray diffraction method of the solid component obtained by removing the liquid medium from the repellent agent 25℃ and the peak intensity A of the maximum peak at the measurement temperature of 55°C 55℃ Diffraction intensity ratio [A 55℃ / A 25℃ 4. The repellent according to any one of items 1 to 3, wherein the value of [R] is 0.5 or more. [Section 5] Item 5. The repellent according to any one of Items 1 to 4, wherein the modified polyol has four or more optionally substituted monovalent hydrocarbon groups having from 20 to 40 carbon atoms. [Section 6] Item 6. The repellent according to item 5, wherein the optionally substituted monovalent hydrocarbon group having from 20 to 40 carbon atoms is an alkyl group. [Section 7] The polyol modification modifies four or more hydroxy groups of the polyol to the formula: -YZ n [In the formula, Y is Y 1 and Y 2 is a 1+n valent group consisting of one or more selected from the group consisting of Y 1 is a group consisting of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, -C(OR')R'-, -C(OR')(-)2, -N(-)2 (wherein R' is independently at each occurrence a hydrogen atom or an organic group having 1 to 30 carbon atoms); Y 2is a group consisting of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent aromatic hydrocarbon rings, and optionally substituted di- to tetravalent heterocycles, Z is a monovalent hydrocarbon group having 20 to 40 carbon atoms which may have a substituent, n is an integer between 1 and 3. Item 7. The repellent according to any one of items 1 to 6, which is a compound substituted with a group represented by the following formula: [Section 8] Y -OY 11 -or -OY 11 -Y 21 -Y 12 - wherein each symbol represents independently at each occurrence: Y 11 is a direct bond, -C(=O)-, -C(=O)-NR'-, or -C(=S)-NR'-; Y 21 is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, Y 12 is -O-, -OC(=O)-, -OC(=O)-O-, -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO2-, -SO2NR'-, -C(OR')R'-, or -C(OR')(-)2. Item 8. The repellent according to Item 7, [Section 9] Item 9. The repellent according to any one of items 1 to 8, 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 hydroxy group-containing compound polymers. [Section 10] The polyol is Glucose, fructose, galactose, xylose; Sucrose, cycloamylose, cyclodextrin, maltose, trehalose, lactose, sucralose; Sorbitol, maltitol, erythritol, isomalt, lactitol, mannitol, xylitol, sorbitan, lactitol; Starch, Cellulose, Curdlan, Pullulan, Alginic Acid, Carrageenan, Guar Gum, Chitin, Chitosan, Locust Bean Gum, Kappa Carrageenan, Iota Carrageenan, Isomaltodextrin, Gellan Gum, Tamarind Seed Gum; Ascorbic acid, kojic acid, quinic acid, chlorogenic acid, gluconic acid; Glucosamine; Inositol; Catechins, quercetin, anthocyanins; Ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, glycerol, trimethylolpropane, trimethylolethane; Item 10. The repellent according to any one of items 1 to 9, which is at least one selected from the group consisting of polyglycerin, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymers, hydroxypropyl (meth)acrylate polymers, and hydroxybutyl (meth)acrylate polymers. [Section 11] Item 11. The repellent according to any one of items 1 to 10, wherein the volumetric abundance ratio of particles having a size of 100 μm or more is 25% or less as measured by a laser diffraction scattering method. [Section 12] Item 12. The repellent according to any one of items 1 to 11, wherein the bio-based ratio of the modified polyol is 20% or more. [Section 13] The polyol modification is achieved by modifying the hydroxyl group of the polyol with the formula: -YZ n [In the formula, Y -OY 11 -or -OY 11 -Y 21-Y 12 - wherein each symbol represents independently at each occurrence: Y 11 is a direct bond, -C(=O)-, -C(=O)-NR'-, or -C(=S)-NR'-; Y 21 is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, Y 12 is -O-, -OC(=O)-, -OC(=O)-O-, -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO2-, -SO2NR'-, -C(OR')R'-, or -C(OR')(-)2. and Z is a hydrocarbon group having 6 to 40 carbon atoms, n is an integer between 1 and 3. is a compound substituted with a group represented by The polyol is Glucose, fructose, galactose, xylose; Sucrose, cycloamylose, cyclodextrin, maltose, trehalose, lactose, sucralose; Sorbitol, maltitol, erythritol, isomalt, lactitol, mannitol, xylitol, sorbitan, lactitol; Starch, Cellulose, Curdlan, Pullulan, Alginic Acid, Carrageenan, Guar Gum, Chitin, Chitosan, Locust Bean Gum, Kappa Carrageenan, Iota Carrageenan, Isomaltodextrin, Gellan Gum, Tamarind Seed Gum; Ascorbic acid, kojic acid, quinic acid, chlorogenic acid, gluconic acid; Glucosamine; Inositol; Catechins, quercetin, anthocyanins; Ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, glycerol, trimethylolpropane, trimethylolethane; At least one selected from the group consisting of polyglycerin, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymers, hydroxypropyl (meth)acrylate polymers, and hydroxybutyl (meth)acrylate polymers; Item 13. The repellent according to any one of items 1 to 12, wherein the hydroxy group substitution rate in the modified polyol is 30% or more. [Section 14] The polyol modification product is a polyglycerol having a degree of polymerization of 5 to 15, or a sugar alcohol having a hydroxy group represented by the following formula: -OC(=O)-Z, or -OC(=O)NH-Z [In the formula, Z is an alkyl group having 20 to 24 carbon atoms. is a compound substituted with a group represented by Item 14. The repellent according to any one of items 1 to 13, wherein the hydroxy group substitution rate in the modified polyol is 50% or more. [Section 15] Item 15. The repellent according to any one of items 1 to 14, which is for textile products or paper products. [Section 16] Item 16. A product treated with the repellent according to any one of items 1 to 15. [Section 17] Item 17. The product according to item 16, which is a textile product or a paper product. [Section 18] Item 18. The product according to item 16 or 17, which is greaseproof or waterproof paper. [Section 19] Item 19. The product according to any one of items 16 to 18, which is a food packaging material or a food container. [Section 20] Item 16. A method for producing a treated product, comprising a step of treating a substrate with the repellent according to any one of items 1 to 15. [Section 21] Item 21. The method according to item 20, wherein the treatment is an internal addition treatment. Effect of the Invention

[0007] The repellent of the present disclosure can impart good liquid repellency (especially oil resistance) to paper products. [Brief description of the drawings]

[0008] [Figure 1] 1 shows the results of a variable-temperature X-ray diffraction measurement of a solid component obtained by removing the liquid medium from the repellent in Example 1. [Diagram 2] 1 shows the results of a variable-temperature X-ray diffraction measurement of a solid component obtained by removing the liquid medium from the repellent in Example 2. [Diagram 3] 1 shows the results of a variable-temperature X-ray diffraction measurement of a solid component obtained by removing the liquid medium from the repellent in Example 3. [Figure 4] 1 shows the results of a variable-temperature X-ray diffraction measurement of a solid component obtained by removing the liquid medium from the repellent agent in Comparative Example 1. [Diagram 5] 1 shows the results of a variable-temperature X-ray diffraction measurement of a solid component obtained by removing the liquid medium from the repellent agent in Comparative Example 2. [Figure 6] 13 shows the results of a variable-temperature X-ray diffraction measurement of a solid component obtained by removing the liquid medium from the repellent agent in Comparative Example 3. [Figure 7] 13 shows the results of a variable-temperature X-ray diffraction measurement of a solid component obtained by removing the liquid medium from the repellent agent in Comparative Example 4. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] <Terminology> As used herein, the term "n-valent group" refers to a group having n bonds, i.e., a group that forms n bonds. The term "n-valent organic group" refers to an n-valent group containing carbon. Such an organic group is not particularly limited, but may be a hydrocarbon group or a derivative thereof. The derivative of a hydrocarbon group refers to a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, halogen, etc. at the end or molecular chain of the hydrocarbon group.

[0010] As used herein, the term "hydrocarbon group" refers to a group containing carbon and hydrogen, which is a group obtained by removing a hydrogen atom from a hydrocarbon. Such a hydrocarbon group includes, but is not limited to, C 1-20 Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. The hydrocarbon group may contain one or more ring structures. The hydrocarbon group may be substituted with one or more substituents, if explicitly stated.

[0011] In this specification, when a term (symbol) that may occur multiple times in a chemical structure is defined, the definition applies independently at each occurrence, unless otherwise stated, regardless of whether "independently at each occurrence," "independently of each other," "independently of each other," or similar expressions are explicitly stated.

[0012] It should be understood that the chemical structures illustrated herein do not encompass chemical structures that would be recognized by those of ordinary skill in the art as being chemically impossible or extremely unstable.

[0013] <Repellent>

[0014] The repellent in the present disclosure imparts liquid repellency (water repellency, oil repellency, oil resistance, and / or water resistance) to a substrate (e.g., a fiber substrate, a paper substrate), and can function as at least one selected from the group consisting of a water repellent, an oil repellent, an oil resistance agent, and a water resistance agent. The repellent in the present disclosure can effectively impart oil resistance (oil repellency) and / or water resistance (water repellency) to the substrate, and can, for example, effectively impart both oil resistance and water resistance.

[0015] The repellent in the present disclosure may be a water-dispersible repellent containing a polyol modification and a dispersant. The repellent in the present disclosure may be a repellent that satisfies one or more of the following (1) and (2). (1) In a differential scanning calorimetry measurement of the polyol modified product or a differential scanning calorimetry measurement of a solid component obtained by removing the liquid medium from the repellent, the temperature of the maximum endothermic peak in the temperature range of 25°C to 180°C is 55°C or higher. (2) The modified polyol has four or more monovalent hydrocarbon groups having 20 to 40 carbon atoms, each of which may have a substituent.

[0016] The repellent agent in the present disclosure may not contain any compound selected from the group consisting of a compound having a fluoroalkyl group having 8 or more carbon atoms, a compound having a perfluoroalkyl group having 8 or more carbon atoms, a compound having a fluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group, a compound having a fluoroalkyl group, and a compound having a fluorine atom. The repellent agent in the present disclosure can impart liquid repellency to a substrate even if it does not contain these fluorine compounds.

[0017] [Volume ratio of particles] The volumetric ratio of particles of 100 μm or more in the repellent of the present disclosure measured by a laser diffraction scattering method may be 25% or less, 20% or less, 15% or less, 10% or less, 5% or less, 3% or less, or 1.5% or less, and is preferably 15% or less, or 5% or less. It is preferable that the volumetric ratio of particles of 100 μm or more is within the above range from the viewpoint of coverage. There is no limitation on the method for making the volumetric ratio of particles of 100 μm or more measured by a laser diffraction scattering method 25% or less, but for example, the particles in the raw material and / or dispersion may be finely divided using a grinder, homogenizer, etc.

[0018] [Volume Median Diameter] The volume median diameter of the repellent of the present disclosure measured by the laser diffraction scattering method may be 10 nm or more, 30 nm or more, 50 nm or more, or 100 nm or more, preferably 150 nm or more or 200 nm or more, and may be 100 μm or less, 90 μm or less, 80 μm or less, 70 μm or less, 60 μm or less, 50 μm or less, 40 μm or less, 30 μm or less, 20 μm or less, or 10 μm or less, preferably 30 μm or less or 25 μm or less. In the present disclosure, the volume median diameter refers to the median diameter (D50) in the volume-based particle size distribution measured by the laser diffraction scattering method.

[0019] [Differential Scanning Calorimetry] In differential scanning calorimetry of the solid component obtained by removing the liquid medium from the repellent of the present disclosure, the maximum endothermic peak temperature in the temperature range of 25°C to 180°C is preferably 55°C or higher. This allows the effects of the present disclosure to be more effectively achieved. The maximum endothermic peak temperature may be 55°C or higher, 60°C or higher, or 65°C or higher. The maximum endothermic peak temperature may be 100°C or lower, 90°C or lower, 80°C or lower, or 70°C or lower.

[0020] [Variable temperature X-ray diffraction measurement] In a variable temperature X-ray diffraction measurement of the solid component obtained by removing the liquid medium from the repellent agent of the present disclosure, the peak intensity A of the maximum peak at a measurement temperature of 25°C in the 2θ range of 15° to 30° is 25℃ and the peak intensity A of the maximum peak at the measurement temperature of 55°C55℃ Diffraction intensity ratio [A 55℃ / A 25℃ ] is preferably 0.5 or more. 55℃ / A 25℃ may be 0.6 or more, 0.7 or more, 0.8 or more, 0.9 or more, 1.0 or more, or 1.1 or more, preferably 0.8 or more or 0.9 or more, and may be 3 or less, 2.75 or less, 2.5 or less, 2.35 or less, or 2.0 or less. By being within the above range, for example, being equal to or greater than the above lower limit, the arrangement structure of the alkyl chains can be maintained even in a high temperature range, and the effects of the present disclosure can be more effectively achieved.

[0021] [Modified polyol] The modified polyol in the present disclosure is capable of adhering to a substrate and imparting liquid repellency to the substrate.

[0022] [Characteristics of modified polyols] The HD (n-hexadecane) contact angle of the polyol-modified product may be 10° or more, 15° or more, 25° or more, 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, or 65° or more, preferably 30° or more, and may be 100° or less, 90° or less, or 75° or less. When the polyol-modified product has an HD contact angle equal to or greater than the above lower limit, it can impart good liquid repellency (especially oil repellency) to the substrate. The HD contact angle is the static contact angle of the polyol-modified product with respect to the spin-coated film as shown in the examples, and is obtained by dropping 2 μL of HD on the spin-coated film and measuring the contact angle 1 second after the drop lands.

[0023] The water contact angle of the polyol-modified product may be 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 65° or more, 75° or more, 85° or more, 90° or more, or 100° or more, and may be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. When the polyol-modified product has a water contact angle equal to or greater than the above lower limit, it can impart good liquid repellency (particularly water repellency) to the substrate. The water contact angle is the static contact angle of the polyol-modified product with respect to the spin-coated film as shown in the examples, and is obtained by dropping 2 μL of water onto the spin-coated film and measuring the contact angle 1 second after the drop lands.

[0024] The polyol modification is preferably a compound having carbon of bio-based origin. The bio-based degree is measured in accordance with ASTM D6866. The bio-based degree may be 20% or more, preferably 30% or more, more preferably 50% or more, even more preferably 60% or more, even more preferably 70% or more, and most preferably 80% or more or 90% or more, for example 100%. A high bio-based degree means that a small amount of fossil resource-based materials, such as petroleum, is used, and from this perspective, the higher the bio-based degree of the polyol modification, the more preferable it is.

[0025] The polyol modification preferably has a biodegradability of 5% or more. Since the environmental load is reduced, the higher the biodegradability, the more preferable. The biodegradability of the polyol modification 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, and is preferably 60% or more, more preferably 70% or more, even more preferably 80% or more, and most preferably 90% or more. Such biodegradability may be the biodegradability at 180 days as specified in JIS K 6953-1 or ASTM D6400.

[0026] The modified polyol may not have any one selected from the group consisting of a fluoroalkyl group having 8 or more carbon atoms, a perfluoroalkyl group having 8 or more carbon atoms, a fluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group, a fluoroalkyl group, and a fluorine atom. Even if the modified polyol does not contain these fluorine-containing groups, it can impart liquid repellency to the substrate.

[0027] In differential scanning calorimetry of the modified polyol, the maximum endothermic peak temperature in the temperature range of 25°C to 180°C is preferably 55°C or higher. This allows the effects of the present disclosure to be more effectively achieved. The maximum endothermic peak temperature may be 55°C or higher, 60°C or higher, or 65°C or higher. The maximum endothermic peak temperature may be 100°C or lower, 90°C or lower, 80°C or lower, or 70°C or lower.

[0028] The polyol modified product is a polymer having a degree of polymerization of at least 1. From the viewpoint of improving liquid repellency, the degree of polymerization of the polyol modified product may be 2 or more, 3 or more, 5 or more, 6 or more, preferably 7 or more, more preferably 8 or more, and even more preferably 9 or more, and from the viewpoint of improving the handleability of the repellent, it may be 100 or less, preferably 50 or less, more preferably 30 or less, even more preferably 15 or less, and particularly preferably 12 or less. The degree of polymerization means the number of repeating monomer units constituting the polymer.

[0029] The degree of polymerization in the present disclosure means an average degree of polymerization. The average degree of polymerization in the present disclosure means a degree of polymerization measured under the following conditions. In the present disclosure, when the polyol modified product is a polyglycerin modified product obtained by modifying polyglycerin, the degree of polymerization of the polyol modified product means the average degree of polymerization of the polyglycerin. The average degree of polymerization of polyglycerin is the average degree of polymerization (n) calculated from the hydroxyl value by the terminal group analysis method. In detail, the average degree of polymerization and the average molecular weight are calculated from the following formulas (Formula 1) and (Formula 2). (Formula 1) Average molecular weight=74n+18 (Equation 2) Hydroxyl value = 56110 (n + 2) / average molecular weight The hydroxyl value in the above formula (2) is a numerical value that is an index of the number of hydroxyl groups contained in polyglycerol. The hydroxyl value is calculated from the amount of potassium hydroxide required to neutralize the acetic acid required to acetylate the free hydroxyl groups contained in 1 g of polyglycerol, and is calculated in accordance with "Standard Methods for Analysis of Fats, Oils and Related Compounds (I), 2003 Edition, Established by the Japan Oil Chemists' Society." The hydroxyl value of the raw material polyglycerol is actually measured according to the above-mentioned Standard Methods for Analysis of Fats, Oils and Related Compounds, and the average degree of polymerization and average molecular weight of polyglycerol can be calculated from the above-mentioned formula.

[0030] In the present disclosure, when the polyol modified product is a polyvinyl alcohol modified product obtained by modifying polyvinyl alcohol, the degree of polymerization of the polyol modified product means the average degree of polymerization of the polyvinyl alcohol. The average degree of polymerization of polyvinyl alcohol can be measured in accordance with JIS K 6726 polyvinyl alcohol test method.

[0031] In the present disclosure, when the polyol-modified product is a polysaccharide-modified product obtained by modifying a polysaccharide, the degree of polymerization of the polyol-modified product means the average degree of polymerization of the polysaccharide. The average degree of polymerization of a polysaccharide can be analyzed as follows. The degree of polymerization is the number of monosaccharide units (fructose and glucose units) in the polysaccharide, and the average degree of polymerization is, for example, the average degree of polymerization determined by the top of the peaks of each analysis result obtained by a normal analysis method such as HPLC, GC, and HPAEC as follows. The measurement can be performed by using, for example, ULTRON PS-80N (8×300 mm) (solvent: water, flow rate: 0.5 ml / min, temperature: 50° C.) manufactured by Shinwa Chemical Industry Co., Ltd. or TSK-GEL G30000 PWXL (7.8×300 mm) (solvent: water, flow rate: 0.5 ml / min, temperature: 50° C.) manufactured by TOSOH Co., Ltd. as a column, and a differential refractometer as a detector.

[0032] The polyol modification may be low molecular weight (e.g., weight average molecular weight less than 1500, less than 1000, 500 or less) and / or high molecular weight. The weight average molecular weight of the polyol modification may be 100 or more, 300 or more, 500 or more, 1000 or more, 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more, and may be 1000000 or less, 750000 or less, 500000 or less, 300000 or less, 100000 or less, 750000 or less, 500000 or less, 30000 or less, 100000 or less, 5000 or less, 30000 or less, 2000 or less, 1000 or less, or 500 or less.

[0033] The substitution rate of the hydroxyl group in the modified polyol may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 100%, preferably 10% or more, for example 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, particularly 80% or more, and may be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, 15% or less, for example 95% or less. Here, the "substitution rate" means the proportion (mol%) of the hydroxyl group derived from the polyol that is modified, and may mean the proportion (mol%) of the hydroxyl group that is modified with a monovalent hydrocarbon group having 1 to 40 carbon atoms (for example, 20 to 40 carbon atoms) that may have a substituent.

[0034] The residual rate of hydroxyl groups in the polyol modification may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, for example, 5% or more, and may be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, 15% or less, or 5% or less, for example, 50% or less, 30% or less, or 10% or less. Here, the "residual rate" refers to the proportion (mol%) of hydroxyl groups derived from the polyol that are not modified.

[0035] The number of modifying groups (monovalent hydrocarbon groups having 1 to 40 carbon atoms (e.g., 20 to 40 carbon atoms)) possessed by the polyol modified product may be 2 or more, 4 or more, 5 or more, 7 or more, 8 or more, 9 or more, 10 or more, 12 or more, 15 or more, 30 or more, or 50 or more, and may be 1,000 or less, 750 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less.

[0036] The modifying group equivalent of the polyol modified product may be 150 or more, 250 or more, 350 or more, 450 or more, 550 or more, 650 or more, 750 or more, or 1000 or more, and may be 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, or 400 or less. This is the value obtained by dividing the weight average molecular weight of the polyol modified product by the number of modifying groups.

[0037] [Modifying group structure] In the modified polyol, one or more hydroxyl groups of the polyol are substituted with a modifying group. From the viewpoint of improving liquid repellency, the modifying group may have a monovalent hydrocarbon group having 1 to 40 carbon atoms (e.g., 20 to 40 carbon atoms) which may have a substituent.

[0038] (Optionally substituted monovalent hydrocarbon group) The hydrocarbon group used to modify the polyol of the modified polyol is a monovalent hydrocarbon group which may have a substituent.

[0039] The hydrocarbon group may be a monovalent hydrocarbon group having 1 to 40 carbon atoms (e.g., 20 to 40 carbon atoms). The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be branched, cyclic, or linear, and is more preferably linear.

[0040] 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, 22 or more, 24 or more, 26 or more, or 28 or more, and is preferably 6 or more, 10 or more, 12 or more, or 16 or more, and may be 40 or less, 35 or less, 30 or less, or 25 or less, and is preferably 35 or less, or 30 or less.

[0041] The hydrocarbon group may have a substituent, but is preferably unsubstituted. Examples of the substituent include -OR', -N(R')2, -COOR', and halogen atoms (wherein R' is independently a hydrogen atom or an organic group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms (e.g., a hydrocarbon group, particularly an aliphatic hydrocarbon group) in each occurrence). The substituent may or may not have active hydrogen. The number of the substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the hydrocarbon group having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0042] (-YZ n ) In the present disclosure, modified polyols are those in which one or more of the hydroxy groups of the polyol has the formula: -YZ n [In the formula, Y is Y 1 and Y 2 is a 1+n valent group consisting of one or more selected from the group consisting of Y 1 is a group consisting of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, -C(OR')R'-, -C(OR')(-)2, -N(-)2 (wherein R' is independently in each occurrence a hydrogen atom or an organic group (e.g., a hydrocarbon group, particularly an aliphatic hydrocarbon group) having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms), Y 2 is a group consisting of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent aromatic hydrocarbon rings, and optionally substituted di- to tetravalent heterocycles, Z is a monovalent hydrocarbon group having 1 to 40 carbon atoms (e.g., 20 to 40 carbon atoms) which may have a substituent; n is an integer between 1 and 3. is substituted with a group represented by the following formula:

[0043] (Y) Y is Y 1 and Y 2 is a 1+n valent group consisting of one or more selected from the group consisting of Y 1 is a group consisting of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, -C(OR')R'-, -C(OR')(-)2, -N(-)2 (wherein R' is independently in each occurrence a hydrogen atom or an organic group (e.g., a hydrocarbon group, particularly an aliphatic hydrocarbon group) having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms), Y 2is a group composed of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent aromatic hydrocarbon rings, and optionally substituted di- to tetravalent heterocycles.

[0044] n is the number of Zs bonded to Y, and may be an integer of 1 to 3. n may be 1 or more, 2 or more, or 3 or more, and may be 3 or less, 2 or less, or 1 or less, for example, 2 or less.

[0045] The molecular weight of Y may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more; and may be 3000 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less.

[0046] ○ Y 1 Y 1 is a non-hydrocarbon linker.

[0047] Y 1 is a direct bond or a divalent or higher group. 1 The valence of Y may be 2 to 4, 2 to 3, or 2. 1 is preferably not only a direct bond.

[0048] Y 1 The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0049] Y 1may be composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -S(=O)2-, -NR'-, -C(OR')R'-, and -C(OR')(-)2 (wherein R' is independently in each occurrence a hydrogen atom or an organic group (e.g., a hydrocarbon group, particularly an aliphatic hydrocarbon group) having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms). Y 1 Examples include: direct binding, -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO2-, -SO2NR'-, -C(OR')R'-, -C(OR')(-)2 etc. (In the formula, R' in each occurrence is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) (e.g., a hydrocarbon group, particularly an aliphatic hydrocarbon group).) Examples include:

[0050] ○ Y 2 Y 2 is a linker of a hydrocarbon ring which may have a substituent, a hydrocarbon aromatic ring which may have a substituent, or a heterocycle which may have a substituent.

[0051] Y 2 Y may be a hydrocarbon group or a non-hydrocarbon group (including heteroatoms). 2 Y may be aliphatic or aromatic. 2 may be linear, branched or cyclic.

[0052] Y 2 is a divalent or higher group. 2 The valency of may be, for example, 2 to 4, 2 to 3, or 2.

[0053] Y 2 may have 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more; and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[0054] Y 2 is composed of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent aromatic hydrocarbon rings, and optionally substituted di- to tetravalent heterocycles.

[0055] The divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or straight chain hydrocarbon group. The divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group having 1 to 40 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more, and may be 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less. The valence of the aliphatic hydrocarbon group may be 2 or more, 3 or more, or 4, and may be 4 or less, 3 or less, or 2.

[0056] The aliphatic hydrocarbon group may have a substituent. Examples of the substituent include -OR', -N(R')2, -COOR', and a halogen atom (wherein R' is, independently at each occurrence, a hydrogen atom or an organic group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms (e.g., a hydrocarbon group, particularly an aliphatic hydrocarbon group)). The substituent may or may not have active hydrogen. The number of the substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the aliphatic hydrocarbon group having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0057] Examples of divalent to tetravalent hydrocarbon aromatic rings include groups obtained by removing 2 to 4 hydrogen atoms from a hydrocarbon aromatic ring such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthacene), pentacene, pyrene, and coronene. The number of ring-constituting atoms of the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12, and preferably 5 to 12. The valence of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0058] The aromatic hydrocarbon ring may have a substituent. Examples of the substituent include -R', -OR', -N(R')2, -COOR', and halogen atoms (wherein R' is independently a hydrogen atom or an organic group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms (e.g., a hydrocarbon group, particularly an aliphatic hydrocarbon group) in each occurrence). The substituent may or may not have active hydrogen. The number of the substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the aromatic hydrocarbon ring having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0059] The divalent to tetravalent heterocycle may be an aliphatic group or an aromatic group. Examples of the divalent to tetravalent heterocycle include groups obtained by removing 2 to 4 hydrogen atoms from pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, etc. The number of ring-constituting atoms of the heterocycle is 3 to 20, 4 to 16, or 5 to 12, and preferably 5 to 12. The valence of the heterocycle may be 2 or more, 3 or more, or 4, and may be 4 or less, 3 or less, or 2.

[0060] The heterocycle may have a substituent. Examples of the substituent include -R', -OR', -N(R')2, -COOR', and a halogen atom (wherein R' is, independently at each occurrence, a hydrogen atom or an organic group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms (e.g., a hydrocarbon group, particularly an aliphatic hydrocarbon group)). The substituent may or may not have active hydrogen. The number of the substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the heterocycle having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, for example, 65 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less.

[0061] Y 2 Examples include: -Ali- -Cy- -Ali(-)2 -Cy(-)2 (-)2Ali- (-)2Cy- (-)2Ali(-)2 (-)2Cy(-)2 -Ali-Cy- -Cy-Ali- -Cy-Ali-Cy- -Ali-Cy-Ali- [In the formula, Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and Cy is a hydrocarbon aromatic ring or heterocycle.] etc.

[0062] Y 2 Examples of specific examples include: -(CH2) p - (p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and having an unsaturated bond, a hydrocarbon group having a branched structure and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH2) q -Cy-(CH2) r -(q and r each independently represent an integer of 0 to 20, for example, 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle). etc.

[0063] (Example of Y) Examples of Y are described below. In the following, R' is independently in each occurrence a hydrogen atom or an organic group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) (e.g., a hydrocarbon group, particularly an aliphatic hydrocarbon group).

[0064] An example of Y is -Y when Y is bivalent. 1 -, -Y 1 -Y 2 -, -Y 1 -Y 2 -Y 1 -, -Y 1 -Y 2 -Y 1 -Y 2 -, -Y 2 -, -Y 2 -Y 1 -, -Y 2 -Y 1 -Y 2 -, -Y 2 -Y 1 -Y 2 -Y 1 --etc.

[0065] An example of Y is -Y when Y is trivalent. 1 (-)2, -Y 1 -Y 2 (-)2, -Y 1 -(Y 2 -)2, -Y 1 -Y 2 -Y 1 (-)2, -Y 1 -Y 2 (-Y 1 -)2, -Y 1 -(Y 2 -Y 1 -)2, -Y1 -Y 2 -Y 1 -Y 2 (-)2, -Y 1 -Y 2 -Y 1 -(Y 2 -) 2、 -Y 1 -Y 2 -(Y 1 -Y 2 -) 2、 -Y 1 -(Y 2 -Y 1 -Y 2 )2; -Y 2 (-)2, -Y 2 -Y 1 (-)2, -Y 2 -(Y 1 )2, -Y 2 -Y 1 -Y 2 (-)2, -Y 2 -Y 1 (-Y 2 )2, -Y 2 -(Y 1 -Y 2 )2, -Y 2 -Y 1 -Y 2 -Y 1 (-)2, -Y 2 -Y 1 -Y 2 -(Y 1 ) 2、 -Y 2 -Y 1 -(Y 2 -Y 1 ) 2、 -Y 2 -(Y 1 -Y 2 -Y 1 )2; etc. can be mentioned.

[0066] As an example of Y, when Y is tetravalent, -Y 1 (-)3, -Y 1 -Y 2 (-)3, -Y 1 -(Y 2 )3, -Y 1 -Y2 -Y 1 (-)3, -Y 1 -Y 2 (-Y 1 (-)3, -Y 1 -(Y 2 -Y 1 (-)3, -Y 1 -Y 2 -Y 1 -Y 2 (-)3, -Y 1 -Y 2 -Y 1 -(Y 2 -) 3、 -Y 1 -Y 2 -(Y 1 -Y 2 -) 3、 -Y 1 -(Y 2 -Y 1 -Y 2 (-)3; -Y 2 (-)3, -Y 2 -Y 1 (-)3, -Y 2 -(Y 1 (-)3, -Y 2 -Y 1 -Y 2 (-)3, -Y 2 -Y 1 (-Y 2 (-)3, -Y 2 -(Y 1 -Y 2 (-)3, -Y 2 -Y 1 -Y 2 -Y 1 (-)3, -Y 2 -Y 1 -Y 2 -(Y 1 -) 3、 -Y 2 -Y 1 -(Y 2 -Y 1 -) 3、 -Y 2 -(Y 1 -Y 2 -Y 1 (-)3; include the following.

[0067] Preferred examples of Y include -Y 1 -, -Y 1 -Y 2 -, -Y 1 -Y 2 -Y 1 -, -Y 1 -Y 2 (-)2, -Y 2 -, -Y 2 -Y 1 -, -Y 2 -Y 1 -Y 2 -, -Y 2 -Y 1 (-)2, etc.

[0068] (Examples of preferred Y) Preferably, Y is -OY 11 -or -OY 11 -Y 21 -Y 12 - wherein each symbol represents independently at each occurrence: Y 11 is a direct bond, -C(=O)-, -C(=O)-NR'-, or -C(=S)-NR'-; Y 21 is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, Y 12 is -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO2-, -SO2NR'-, -C(OR')R'-, or -C(OR')(-)2. It may be.

[0069] Y 11 is a non-hydrocarbon linker, which is a direct bond or a divalent or higher group.

[0070] Y11 The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0071] Y 11 may be a direct bond, -C(=O)-, -C(=O)-NR'-, or -C(=S)-NR'-.

[0072] Y 21 is a divalent hydrocarbon linker, which may be a hydrocarbon group having 1 to 40 carbon atoms.

[0073] Y 21 may have 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more; and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[0074] Here, the hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or straight chain hydrocarbon group, and may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The hydrocarbon group may have a substituent. Examples of the substituent include -OR', -N(R')2, -COOR', and a halogen atom (wherein R' is independently a hydrogen atom or an organic group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms (e.g., a hydrocarbon group, particularly an aliphatic hydrocarbon group) in each occurrence). The substituent may or may not have an active hydrogen. The number of the substituent may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the substituted hydrocarbon group, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, and preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0075] Y 21Specific examples include: -(CH2) p - (p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and having an unsaturated bond, a hydrocarbon group having a branched structure and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH2) q -Cy-(CH2) r -(q and r each independently represent an integer of 0 to 20, for example, 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle). etc.

[0076] Y 12 may be -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.

[0077] [Z] Z is a monovalent hydrocarbon group having 1 to 40 carbon atoms (e.g., 20 to 40 carbon atoms) which may have a substituent, and the above description of (monovalent hydrocarbon group which may have a substituent) is incorporated herein. The number of carbon atoms in the hydrocarbon group is preferably 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, and preferably 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less. The hydrocarbon group may also contain an unsaturated bond, and the number of unsaturated bonds is preferably 4 or less, 2 or less, or 1. The substituent is preferably OH (hydroxy group).

[0078] [Other modifying groups] The hydroxyl group of the polyol is -YZ n Examples of modifying groups are anionic and / or cationic groups.

[0079] The anionic group may be a monomer having a carboxyl group, a sulfonic acid group, or a phosphoric acid group.

[0080] Salts of anionic groups include alkali metal salts, alkaline earth metal salts, or ammonium salts, such as methylammonium salts, ethanolammonium salts, and triethanolammonium salts.

[0081] The cationic group is an amino group, preferably a tertiary amino group and a quaternary amino group. In the tertiary amino group, the two groups bonded to the nitrogen atom are preferably the same or different and are an aliphatic group having 1 to 5 carbon atoms (particularly an alkyl group), an aromatic group having 6 to 20 carbon atoms (aryl group), or an araliphatic group having 7 to 25 carbon atoms (particularly an aralkyl group, for example, a benzyl group (C6H5-CH2-)). In the quaternary amino group, the three groups bonded to the nitrogen atom are preferably the same or different and are an aliphatic group having 1 to 5 carbon atoms (particularly an alkyl group), an aromatic group having 6 to 20 carbon atoms (aryl group), or an araliphatic group having 7 to 25 carbon atoms (particularly an aralkyl group, for example, a benzyl group (C6H5-CH2-)). In the tertiary amino group and the quaternary amino group, the remaining group bonded to the nitrogen atom may have a carbon-carbon double bond. The cationic group may be in the form of a salt.

[0082] The cationic group that is a salt is a salt with an acid (organic acid or inorganic acid). Organic acids, for example, carboxylic acids having 1 to 20 carbon atoms (particularly, monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and stearic acid) are preferred.

[0083] [Manufacturing method] The modified polyol may be prepared by reacting a modifying agent having a modifying group (or a precursor structure of the modifying group) with a hydroxy group of the polyol.

[0084] (Polyol) A polyol is a compound having two or more hydroxyl groups, and is a compound that is a raw material for a modified polyol. A polyol is a compound having two or more hydroxyl groups in the molecule. The polyol may be aliphatic or aromatic, but is preferably aliphatic.

[0085] The polyol may have an ether bond. Preferably, the polyol may have two or more ether bonds. Specifically, the polyol is preferably a compound having two or more hydroxy groups and two or more ether bonds. In other words, the polyol is preferably a polyether having two or more hydroxy groups.

[0086] When the polyol is a polymer, it may have a hydroxy group and an ether bond in the repeating structure of the monomer unit.

[0087] The polyol may be low molecular weight (e.g., weight average molecular weight less than 1000, 500 or less) and / or high molecular weight. The weight average molecular weight of the polyol may be 50 or more, 100 or more, 300 or more, 500 or more, 1000 or more, 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more, and may be 1000000 or less, 750000 or less, 500000 or less, 300000 or less, 100000 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, 2000 or less, 1000 or less, or 500 or less.

[0088] The number of hydroxy groups in the polyol may be 2 or more, 5 or more, 7 or more, 10 or more, 15 or more, 30 or more, 50 or more, or 100 or more, and may be 3000 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less.

[0089] The hydroxy group equivalent of the polyol may be 20 or more, 40 or more, 60 or more, 80 or more, 100 or more, 120 or more, or 150 or more, and may be 1000 or less, 800 or less, 600 or less, 400 or less, 200 or less, 100 or less, or 75 or less. The hydroxy group equivalent of the polyol is the value obtained by dividing the weight average molecular weight of the polyol by the number of hydroxyl groups.

[0090] The polyol may be a natural product. The natural product may be a high molecular weight natural product, a low molecular weight natural product, or a derivative thereof. The above natural products also include compounds converted from microorganisms. Examples of polyols include monosaccharides, oligosaccharides, polysaccharides, sugar alcohols (reducing sugars), hydroxy acids, amino acids, vitamins, flavonols, hydroxy hydrocarbons, hydroxy group-containing compound polymers, polyether polyols, polymer polyols, polyester polyols, and other polyols.

[0091] Examples of monosaccharides include glucose, fructose, galactose, xylose, and the like.

[0092] Examples of oligosaccharides include sucrose, cycloamylose, cyclodextrin, maltose, trehalose, lactose, and sucralose.

[0093] Examples of sugar alcohols (reducing sugars) include sorbitol, maltitol, erythritol, glycerin, isomalt, lactitol, mannitol, xylitol, sorbitan, and lactitol.

[0094] 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.

[0095] Examples of hydroxy acids include ascorbic acid, kojic acid, quinic acid, chlorogenic acid, gluconic acid, and the like.

[0096] Examples of amino acids include glucosamine.

[0097] Examples of vitamins include ascorbic acid and inositol.

[0098] Examples of flavonols include catechin, quercetin, and anthocyanin.

[0099] Examples of hydroxyhydrocarbons include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, glycerin, trimethylolpropane, trimethylolethane, etc. Hydroxyhydrocarbons are hydrocarbons having a hydroxy group and may be aromatic or aliphatic, but are preferably aliphatic. Hydroxyhydrocarbons may also refer to hydroxyhydrocarbons other than compounds included in other groups such as polysaccharides (other hydroxyhydrocarbons).

[0100] Examples of the hydroxy group-containing compound polymer include polyglycerin, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymer, hydroxypropyl (meth)acrylate polymer, and hydroxybutyl (meth)acrylate polymer.

[0101] An example of a polyether polyol may be a compound obtained by addition polymerization of an alkylene oxide to an initiator. Examples of initiators include compounds having a hydroxyl group with two or more functional groups. Examples of initiators include propylene glycol, polypropylene glycol, ethylene glycol, polyethylene glycol, glycerin, polyglycerin, trimethylolpropane, triethanolamine, pentaerythritol, ethylenediamine, aromatic diamine, diethylenetriamine, sorbitol, and sucrose. Examples of alkylene oxides include ethylene oxide and propylene oxide. Polyether polyols obtained by addition polymerization of an alkylene oxide to the above initiators are also called polyoxyalkylene polyols or oxyalkylene derivatives of polyols. Representative examples of polyether polyols include polyoxypropylene triols obtained by addition polymerization of propylene oxide to glycerin, and polyoxypropylene polyglyceryl ethers obtained by addition polymerization of propylene oxide to polyglycerin.

[0102] An example of a polymer polyol is a compound obtained by polymerizing at least a portion of a polyether polyol with an ethylenically unsaturated monomer, such as acrylonitrile or styrene.

[0103] Examples of polyester polyols may be compounds obtained by dehydration condensation of a compound having a carboxyl group with two or more functional groups and a compound having a hydroxyl group with two or more functional groups. Examples of compounds having a carboxyl group with two or more functional groups include terephthalic acid, isophthalic acid, phthalic acid, methylphthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, succinic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, and acid anhydrides thereof. Examples of compounds having a hydroxyl group with two or more functional groups include ethylene glycol, propylene glycol, propanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and polymers thereof.

[0104] (Modifier) The modifying agent is preferably a compound that is reactive with polyol and has the above-mentioned monovalent hydrocarbon group having 1 to 40 carbon atoms (e.g., 20 to 40 carbon atoms) which may have a substituent.

[0105] Examples of modifying agents are as follows: Acid halide G(O=)CZ Acid anhydride O(C(=O)-Z)2 Carboxylic acid HO(O=)CZ Isocyanate O=C=NZ Thioisocyanate S=C=NZ Epoxy (CH2OCH)CH2O-Z Halide GZ Amine H2N-Z Hydroxy HO-Z [In the formula, Z is as described above, and G is a halogen atom (e.g., F, Cl, Br, or I).]

[0106] Z in the structure of the modifying agent described above may be replaced with any group constituting a modifying group. For example, Z may be a monovalent hydrocarbon group having 1 to 40 carbon atoms (e.g., 20 to 40 carbon atoms) which may have a substituent, or Z may be -YZ n It is also possible to use the following.

[0107] The modified polyol may be synthesized by reacting a polyol with a modifying agent. For example, a modified polyol can be synthesized by reacting a modifying agent that is an acid halide compound, an acid anhydride, or a carboxylic acid with a hydroxy group of a polyol to form an ester bond. Alternatively, a modified polyol can be produced by reacting a modifying agent that is a halide or an epoxy compound with a hydroxy group of a polyol to form an ether bond. Those skilled in the art can appropriately design the reaction conditions between the polyol and the modifying agent, such as using a catalyst (e.g., an acid catalyst or a base catalyst) or using a condensing agent, depending on the target product.

[0108] [Dispersant] The repellent of the present disclosure preferably includes a dispersant.

[0109] The dispersant is selected from organic dispersants and inorganic dispersants. There may be at least one type. The dispersant may be at least one type selected from anionic, nonionic dispersants, cationic dispersants, amphoteric dispersants, and inorganic dispersants. The repellent may not include an anionic dispersant. The dispersant may include a dispersant other than a fatty acid ester having an HLB value of 7 or more. For example, the dispersant may include a fatty acid ester-based dispersant having an HLB value of less than 7, or may include a dispersant other than a fatty acid ester.

[0110] As the dispersant, an organic dispersant and an inorganic dispersant may be used separately, or an organic dispersant and an inorganic dispersant may be used in combination.

[0111] An organic dispersant may be used as the dispersant. The organic dispersant can be classified into a nonionic dispersant, an anionic dispersant, a cationic dispersant, and an amphoteric dispersant, and the organic dispersant may mean a surfactant.

[0112] The dispersant may be fluorine-free.

[0113] [Nonionic dispersant] The dispersant may include a nonionic dispersant. The nonionic dispersant may be a nonionic surfactant.

[0114] The nonionic dispersant may be a low molecular weight or a high molecular weight dispersant. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may be 100,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0115] Examples of nonionic dispersants include ethers, esters, ester ethers, alkanolamides, polyols and amine oxides.

[0116] An example of an ether is a compound having an oxyalkylene group (preferably a polyoxyethylene group).

[0117] An example of the ester is an ester of an alcohol and a fatty acid. An example of the alcohol is a monohydric to tridehydric (particularly dihydric to decahydric) alcohol (e.g., an aliphatic alcohol) having 1 to 50 carbon atoms (particularly 10 to 30 carbon atoms). An example of the fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0118] An example of the ester ether is a compound in which an alkylene oxide (particularly ethylene oxide) is added to an ester of an alcohol and a fatty acid. An example of the alcohol is a monohydric to tridecahydric (particularly dihydric to decahydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms). An example of the fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0119] An example of an alkanolamide is formed from a fatty acid and an alkanolamine. The alkanolamide may be a monoalkanolamide or a dialkanolamine. An example of a fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. The alkanolamine may be an alkanol having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0120] The polyol may be a di- to penta-hydric alcohol having 10 to 30 carbon atoms. The amine oxide may be an oxide (eg, having 5 to 50 carbon atoms) of an amine (secondary amine or preferably tertiary amine).

[0121] The nonionic dispersant is preferably a nonionic dispersant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms in the alkylene group in the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic dispersant is generally preferably 2 to 100.

[0122] 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.

[0123] The nonionic dispersant may be an alkylene oxide adduct of a linear and / or branched aliphatic (saturated and / or unsaturated) group, a polyalkylene glycol ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a sorbitan ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a glycerin ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyglycerin ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a sucrose ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of acetylene glycol, and the like. Among these, those in which the structure of the alkylene oxide adduct portion and the polyalkylene glycol portion is polyoxyethylene (POE) or polyoxypropylene (POP) or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred. Additionally, the nonionic dispersant need not contain aromatic groups.

[0124] The nonionic dispersant has the formula: R 1 O-(CH2CH2O) p -(R 2 O) q -R 3 [In the formula, R 1 is an alkyl group having 1 to 22 carbon atoms or an alkenyl group or acyl group having 2 to 22 carbon atoms, R 2 each is independently the same or different and is an alkylene group having 3 or more carbon atoms (e.g., 3 to 10), R 3 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms, p is a number equal to or greater than 2, q is a number equal to or greater than 0. The compound may be represented by the formula:

[0125] R 1R preferably has 8 to 20 carbon atoms, particularly preferably 10 to 18 carbon atoms. 1 Preferred specific examples include an octyl group, a nonyl group, a trimethylnonyl group, a lauryl group, a tridecyl group, an oleyl group, and a stearyl group. R 2 Examples are a propylene group and a butylene group. In the nonionic dispersant, p may be a number of 3 or more (for example, 5 to 200). q may be a number of 2 or more (for example, 5 to 200). That is, -(R 2 O) q may form a polyoxyalkylene chain. The nonionic dispersant may be a polyoxyethylene alkylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) in the center. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, and a styrene chain, and among these, an oxypropylene chain is preferred.

[0126] Examples of nonionic dispersants include ethylene oxide and hexylphenol, isooctatylphenol, hexadecanol, oleic acid, alkanes (C 12 -C 16 ) Thiol, Sorbitan Mono Fatty Acid (C7-C 19 ) or alkyl(C 12 -C 18 ) amines, etc., sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, lecithin derivatives, etc.

[0127] The proportion of the polyoxyethylene block may be 5 to 80% by weight, for example 30 to 75% by weight, particularly 40 to 70% by weight, based on the molecular weight of the nonionic dispersant (copolymer). The average molecular weight of the nonionic dispersant is generally 300 to 5,000, for example, 500 to 3,000. The nonionic dispersant may be a single type, or a mixture of two or more types. The nonionic dispersant may be a mixture of a compound having an HLB (hydrophilic-hydrophobic balance) of less than 15 (particularly 5 or less) and a compound having an HLB of 15 or more. Specifically, it is preferable to select from polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene, and polyoxypropylenes having an HLB value of 1 to 18, and sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene glycerin fatty acid esters, and polyoxyethylene sorbitan fatty acid esters having an HLB value of less than 7.

[0128] [Cationic dispersants] The dispersant may contain a cationic dispersant. The cationic dispersant may be a cationic surfactant. The cationic dispersant may be a low molecular weight type (e.g., molecular weight of 2000 or less, particularly 10000 or less) or a high molecular weight type (e.g., molecular weight of 2000 or more). The cationic dispersant may be a compound that does not have an amide group.

[0129] The cationic dispersant may be a low molecular weight or a high molecular weight. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may be 100,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0130] The cationic dispersant may be an amine salt, a quaternary ammonium salt, or an oxyethylene adduct ammonium salt.Specific examples of the cationic dispersant include, but are not limited to, amine salt-type dispersants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazoline, and quaternary ammonium salt-type dispersants such as alkyl trimethyl ammonium salts, dialkyl dimethyl ammonium salts, alkyl dimethyl benzyl ammonium salts, pyridinium salts, alkyl isoquinolinium salts, benzethonium chloride, and benzalkonium chloride.

[0131] Preferred examples of the cationic dispersant are R 21 -N + (-R 22 )(-R 23 )(-R 24 )X - [In the formula, R 21 , R 22 , R 23 and R 24 is a hydrocarbon group having 1 to 40 carbon atoms, X is an anionic group. It is a compound represented by the formula: R 21 , R 22 , R 23 and -R 24 Specific examples of X include alkyl groups (e.g., methyl, butyl, stearyl, and palmityl groups). Specific examples of X include halogens (e.g., chlorine) and acids (e.g., hydrochloric acid and acetic acid). The cationic dispersant is particularly preferably a monoalkyltrimethylammonium salt (alkyl having 4 to 40 carbon atoms).

[0132] The cationic dispersant is preferably an ammonium salt. The cationic dispersant has the formula: R 1 p -N + R 2 q X - [In the formula, R 1 is C12 or higher (e.g. C12 ~C 50 ) linear and / or branched aliphatic (saturated and / or unsaturated) groups, R 2 is H or a C1-4 alkyl group, a benzyl group, a polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (particularly 2, particularly 3) to 50); (CH3, C2H5 are particularly preferred), X is a halogen atom (for example), a C1-C4 fatty acid base, p is 1 or 2, q is 2 or 3, and p+q=4. R 1 may have 12 to 50 carbon atoms, for example, 12 to 30 carbon atoms.

[0133] Specific examples of cationic dispersants include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydropolyoxyethylene)ammonium chloride, benzyldodecyldi(hydropolyoxyethylene)ammonium chloride, and N-[2-(diethylamino)ethyl]oleamide hydrochloride.

[0134] [Anionic dispersants] The dispersant may comprise an anionic dispersant. The anionic dispersant may be an anionic surfactant. The dispersant may be free of an anionic dispersant.

[0135] The anionic dispersant may be a low molecular weight or a high molecular weight. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may be 100,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0136] Examples of anionic dispersants include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkanesulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfonic fatty acid salts, N-acylamino acid type dispersants, phosphoric acid mono- or diester type dispersants, and sulfosuccinic acid esters.

[0137] [Amphoteric dispersant] The dispersant may comprise an amphoteric dispersant, which may be an amphoteric surfactant.

[0138] The amphoteric dispersant may be a low molecular weight or a high molecular weight dispersant. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may be 100,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0139] Examples of amphoteric dispersants include alanines, imidazolinium betaines, amido betaines, and betaine acetate. Specific examples include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylamino acetate betaine, and fatty acid amidopropyl dimethylamino acetate betaine.

[0140] [Inorganic dispersant] The dispersant may comprise an inorganic dispersant.

[0141] The average primary particle size of the inorganic dispersant may be 5 nm or more, 30 nm or more, 100 nm or more, 1 μm or more, 10 μm or more, or 25 μm or more, and may be 100 μm or less, 50 μm or less, 10 μm or less, 1 μm or less, 500 nm or less, or 300 nm or less. The average primary particle size can be measured, for example, by observation with a microscope (scanning electron microscope or transmission electron microscope). The inorganic dispersant may be a hydrophilic particle.

[0142] 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.

[0143] [Amount of dispersant] The amount of the dispersant may be, relative to 100 parts by weight of the polyol modified product, 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less.

[0144] [Liquid medium] The repellent in the present disclosure may include a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The repellent may be a dispersion or a solution. The repellent in the present disclosure may be a water-dispersed type and may include at least water.

[0145] Examples of the organic solvent include esters (e.g., esters having 2 to 40 carbon atoms, specifically, ethyl acetate, butyl acetate), ketones (e.g., ketones having 2 to 40 carbon atoms, specifically, methyl ethyl ketone, diisobutyl ketone), alcohols (e.g., alcohols having 1 to 40 carbon atoms, specifically, isopropyl alcohol), aromatic solvents (e.g., toluene and xylene), and petroleum solvents (e.g., alkanes having 5 to 10 carbon atoms, specifically, naphtha, kerosene). The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent may contain a compound having at least one hydroxyl group (e.g., alcohol, polyols such as glycol-based solvents, ethers of polyols (e.g., monoethers), etc.). These may be used alone or in combination of two or more.

[0146] [Amount of liquid medium] The amount of the liquid medium may be, relative to 1 part by weight of the polyol modified product, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less.

[0147] The amount of water may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 1 part by weight of the polyol modified product.

[0148] The amount of the organic solvent may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 1 part by weight of the polyol modified product.

[0149] 〔silicone〕 The repellent in the present disclosure may contain silicone (polyorganosiloxane). By containing silicone, it is possible to obtain good texture and durability in addition to good liquid repellency.

[0150] As the silicone, known silicones can be used, and examples of silicones include polydimethylsiloxane and modified silicones (amino-modified, epoxy-modified silicone, carboxy-modified silicone, methylhydrogen silicone, etc.). The silicone may be a silicone wax having wax-like properties. These may be used alone or in combination of two or more.

[0151] The weight average molecular weight of the silicone may be 1000 or more, 10000 or more, or 50000 or more. The weight average molecular weight of the silicone may be 500000 or less, 2500000 or less, 100000 or less, or 50000 or less.

[0152] [Amount of silicone] The amount of silicone may be, relative to 100 parts by weight of the polyol modified product, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0153] 〔wax〕 The repellent in the present disclosure may contain a wax. By containing a wax, it is possible to impart good liquid repellency to the substrate.

[0154] Examples of waxes include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin wax (polyethylene wax, polypropylene wax, etc.), oxidized polyolefin wax, silicone wax, animal and vegetable wax, mineral wax, etc. Paraffin wax is preferred. Specific examples of compounds constituting the wax include normal alkanes (e.g., tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane), and normal alkenes (e.g., 1-eicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane). The carbon number of the compound constituting the wax is preferably 20 to 60, for example, 25 to 45. The molecular weight of the wax may be from 200 to 2000, for example, from 250 to 1500, or from 300 to 1000. These may be used alone or in combination of two or more.

[0155] The melting point of the wax may be 50° C. or higher, 55° C. or higher, 60° C. or higher, 65° C. or higher, or 70° C. or higher, preferably 55° C. or higher, more preferably 60° C. or higher. The melting point of the wax is measured in accordance with JIS K 2235-1991.

[0156] [Amount of wax] The amount of wax may be, relative to 100 parts by weight of the polyol modified product, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0157] [Organic acid] The repellent of the present disclosure may contain an organic acid. As the organic acid, a known one may be used. As the organic acid, carboxylic acid, sulfonic acid, sulfinic acid, etc. are preferably mentioned, and carboxylic acid is particularly preferable. As the carboxylic acid, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid, etc. are mentioned, and formic acid or acetic acid is particularly preferable. In the present disclosure, the organic acid may be used alone or in combination of two or more kinds. For example, formic acid and acetic acid may be used in combination.

[0158] [Amount of organic acid] The amount of the organic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the polyol modified product. The amount of the organic acid may be adjusted so that the pH of the repellent is 3 to 10, for example, 5 to 9, particularly 6 to 8. The repellent may be acidic (pH 7 or less, for example 6 or less).

[0159] [Hardening agent] The repellent of the present disclosure may include a curing agent (an active hydrogen reactive compound or an active hydrogen containing compound).

[0160] The curing agent (crosslinking agent) in the repellent agent can effectively cure the modified polyol. The curing agent may be an active hydrogen reactive compound or an active hydrogen-containing compound that reacts with the active hydrogen or active hydrogen reactive group of the modified polyol. Examples of the active hydrogen reactive compound are isocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds, and hydrazide compounds. Examples of the active hydrogen-containing compound are hydroxyl group-containing compounds, amino group-containing compounds, carboxyl group-containing compounds, ketone group-containing compounds, hydrazide compounds, and melamine compounds.

[0161] The curing agent may include an isocyanate compound. The isocyanate compound may be a polyisocyanate compound. The polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound acts as a crosslinking agent. Examples of the polyisocyanate compound include aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates. The isocyanate compound may be a blocked isocyanate compound (e.g., a blocked polyisocyanate compound). The blocked isocyanate compound is a compound in which the isocyanate group of the isocyanate compound is masked with a blocking agent to suppress the reaction.

[0162] Examples of aliphatic polyisocyanates are trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-di ... Aliphatic diisocyanates such as cyanatomethyl caproate, and aliphatic triisocyanates such as lysine ester triisocyanate, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane, etc. These may be used alone or in combination of two or more.

[0163] Examples of alicyclic polyisocyanates include alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of alicyclic polyisocyanates include 1,3-cyclopentene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), and 1,3,5-triisocyanatocyclohexane. These may be used alone or in combination of two or more.

[0164] Examples of the araliphatic polyisocyanate are araliphatic diisocyanate and araliphatic triisocyanate.Specific examples of the araliphatic polyisocyanate are 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethylxylylene diisocyanate) or a mixture thereof, and 1,3,5-triisocyanatomethylbenzene.These may be used alone or in combination of two or more.

[0165] Examples of aromatic polyisocyanates are aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates are m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate or a mixture thereof, 2,4- or 2,6-tolylene diisocyanate or a mixture thereof, triphenylmethane-4,4',4''-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate. These may be used alone or in combination of two or more.

[0166] Examples of the polyisocyanate derivatives include various derivatives of the above-mentioned polyisocyanate compounds, such as dimers, trimers, biurets, allophanates, carbodiimides, uretdione, uretoimine, isocyanurates, iminooxadiazinedione, etc. These may be used alone or in combination of two or more.

[0167] These polyisocyanates can be used alone or in combination of two or more. As the polyisocyanate compound, it is preferable to use a blocked polyisocyanate compound (blocked isocyanate), which is a compound in which the isocyanate group of the polyisocyanate compound is blocked with a blocking agent. It is preferable to use a blocked polyisocyanate compound because it is relatively stable even in a solution and can be used in the same solution as the repellent.

[0168] The blocking agent blocks free isocyanate groups. When the blocked polyisocyanate compound is heated to, for example, 100°C or higher, for example, 130°C or higher, the isocyanate group is regenerated and can easily react with the hydroxyl group. Examples of the blocking agent include phenol-based compounds, lactam-based compounds, aliphatic alcohol-based compounds, and oxime-based compounds. The polyisocyanate compounds can be used alone or in combination of two or more kinds.

[0169] The epoxy compound is a compound having an epoxy group. Examples of the epoxy compound include epoxy compounds having a polyoxyalkylene group, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether. The chloromethyl group-containing compound is a compound having a chloromethyl group. An example of the chloromethyl group-containing compound is chloromethyl polystyrene. The carboxyl group-containing compound is a compound having a carboxyl group. Examples of the carboxyl group-containing compound include (poly)acrylic acid and (poly)methacrylic acid.

[0170] Specific examples of the ketone group-containing compound include (poly)diacetone acrylamide and diacetone alcohol. Specific examples of the hydrazide compound include hydrazine, carbohydrazide, adipic acid hydrazide, and the like. Specific examples of the melamine compound include melamine resins and methyl etherified melamine resins.

[0171] [Amount of hardener] The amount of the curing agent may be, relative to 100 parts by weight of the polyol modified product, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0172] [Other ingredients] The repellent may contain other components in addition to the above components. Examples of the other components include polysaccharides, paper strength agents, flocculants, retention aids, coagulants, binder resins, slip prevention agents, sizing agents, paper strength agents, fillers, antistatic agents, preservatives, ultraviolet absorbers, antibacterial agents, deodorants, fragrances, etc. These may be used alone or in combination of two or more. In addition to the above-mentioned components, other components include other water and / or oil repellents, dispersants, texture adjusters, softeners, flame retardants, paint fixing agents, anti-wrinkle agents, drying speed adjusters, crosslinking agents, film-forming agents, compatibilizers, antifreeze agents, viscosity adjusters, UV absorbers, antioxidants, pH adjusters, insect repellents, defoamers, shrink prevention agents, laundry wrinkle prevention agents, shape retention agents, drape retention agents, ironing improvers, whitening agents, whitening agents, fabric softening clay, dye transfer inhibitors such as polyvinylpyrrolidone, polymer dispersants, dirt removers, scum dispersants, fluorescent whitening agents such as 4,4-bis(2-sulfostyryl)biphenyl disodium (Ciba Specialty Chemicals' Chinopearl CBS-X), dye fixatives, and discoloration inhibitors such as 1,4-bis(3-aminopropyl)piperazine. The following can be blended: stain removers, enzymes such as cellulase, amylase, protease, lipase, keratinase, etc. as fiber surface modifiers, foam inhibitors, silk protein powders, their surface modified products or emulsified dispersions (e.g., K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemicals), hydrolyzed silk liquid (Jomo), Silkgen G Soluble S (Ichimaru Falcos)), stain prevention agents (e.g., nonionic polymer compounds consisting of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units (e.g., FR627 manufactured by GOO Chemical Industry Co., Ltd., SRC-1 manufactured by Clariant Japan, etc.), etc. These may be used alone or in combination of two or more.

[0173] [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 nanofiber, cellulose nanofiber, pullulan, etc. The polysaccharide may be a substituted modified polysaccharide (excluding the above-mentioned polyol modified products), in particular a modified polysaccharide into which a hydroxyl group or a cationic group has been introduced.

[0174] [Paper strength agents, flocculants, retention aids or coagulants] Examples of paper strength enhancers, flocculants, retention improvers or coagulants include styrene polymers (styrene / maleic acid polymers, styrene / acrylic acid polymers), urea-formaldehyde polymers, polyethyleneimine, melamine-formaldehyde polymers, polyamidoamine-epichlorohydrin polymers, polyacrylamide polymers, polyamine polymers, polydiallyldimethylammonium chloride, alkylamine-epichlorohydrin condensates, condensates of alkylene dichlorides and polyalkylene polyamines, dicyandiamide-formaldehyde condensates, dimethyldiallylammonium chloride polymers, and olefin / maleic anhydride polymers.

[0175] [Sizing agent] Examples of sizing agents include cellulose-reactive sizing agents, e.g., rosin-based sizing agents such as rosin-based soaps, rosin-based emulsions / dispersions, cellulose-reactive sizing agents, e.g., emulsions / dispersions of acid anhydrides such as alkyl and alkenyl succinic anhydrides (ASA), alkenyl and alkyl ketene dimers (AKD) and polymers, and anionic, cationic and amphoteric polymers of ethylenically unsaturated monomers, e.g., copolymers of styrene and acrylates.

[0176] [Antistatic agent] Examples of the antistatic agent include cationic antistatic agents having cationic functional groups such as quaternary ammonium salts, pyridinium salts, and primary, secondary, and tertiary amino groups; anionic antistatic agents having anionic functional groups such as sulfonates, sulfates, phosphonates, and phosphates; amphoteric antistatic agents such as alkylbetaines and their derivatives, imidazolines and their derivatives, alanines and their derivatives, nonionic antistatic agents such as aminoalcohols and their derivatives, glycerin and its derivatives, and polyethylene glycols and its derivatives. The antistatic agent may be an ion-conductive polymer obtained by polymerizing or copolymerizing monomers having these cationic, anionic, or amphoteric ion-conductive groups. These may be used alone or in combination of two or more.

[0177] [Preservatives] The preservatives are mainly used to enhance the preservative and bactericidal power and maintain the preservative properties during long-term storage. Examples of the preservatives include isothiazolone organic sulfur compounds, benzisothiazolone organic sulfur compounds, benzoic acids, 2-bromo-2-nitro-1,3-propanediol, etc.

[0178] [Ultraviolet absorber] An ultraviolet absorber is a drug that has an ultraviolet protection effect, and is a component that absorbs ultraviolet light and converts it into infrared light, visible light, etc. Examples of ultraviolet absorbers include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole compounds, 4-t-butyl-4'-methoxybenzoylmethane, etc.

[0179] [Antibacterial agents] Antibacterial agents are components that have the effect of suppressing the growth of bacteria on fibers and further suppressing the generation of unpleasant odors resulting from the decomposition products of microorganisms. Examples of antibacterial agents include cationic bactericides such as quaternary ammonium salts, bis-(2-pyridylthio-1-oxide) zinc, polyhexamethylene biguanidine hydrochloride, 8-oxyquinoline, polylysine, etc.

[0180] [Deodorant] Examples of deodorants include cluster dextrin, methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamidopropyldimethylamine oxide, and aminocarboxylic acid metal complexes (zinc complex of trisodium methylglycinediacetate described in WO 2012 / 090580).

[0181] [Amount of other ingredients] The amount or total amount of the other components may be, relative to 100 parts by weight of the polyol modified product, 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0182] <Manufacturing method of treated textile or paper products> The method of making a repellent treated product of the present disclosure includes treating a substrate with the repellent agent described above.

[0183] "Treatment" means that the repellent is applied to the substrate by immersion, spraying, coating, etc. The treatment causes the polyol modifier, which is the active ingredient of the repellent, to adhere to the inside and / or surface of the substrate. Here, the adhesion may be physical adhesion or chemical adhesion, and for example, the polyol modifier may be physically or chemically (by reacting with) the hydroxyl groups of the substrate (fiber, paper, glass, etc.).

[0184] [Base material] The substrate to be treated with the repellent agent of the present disclosure is not limited, but is preferably a textile product or a paper product, in particular a paper product.

[0185] The repellent agent in the present disclosure provides liquid repellency to a substrate (e.g., a fiber substrate, a paper substrate) and can function as at least one selected from the group consisting of a water repellent agent, an oil repellent agent, an oil-resistant agent, and a water-resistant agent. The substrate treated with the repellent agent in the present disclosure is, for example, oil-resistant paper or water-resistant paper.

[0186] Examples of the substrate for textile products include natural fibers of animal and vegetable origin such as cotton, hemp, wool, silk, etc., synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polypropylene, etc., semi-synthetic fibers such as rayon, acetate, etc., inorganic fibers such as glass fiber, carbon fiber, asbestos fiber, etc., or mixtures of these fibers. Textile products include woven fabrics, knitted fabrics and nonwoven fabrics, clothing forms (e.g., water-repellent clothing, e.g., raincoats), and carpets, but the treatment may be performed on fibers, yarns, and intermediate textile products (e.g., slivers or rovings) before being made into cloth.

[0187] Examples of the substrate for paper products include paper made of bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulp such as groundwood pulp, mechanical pulp or thermomechanical pulp, waste paper pulp such as recycled newsprint, recycled magazine paper, recycled corrugated cardboard or deinked recycled paper, containers made of paper, molded articles made of paper, etc. Specific examples of paper products include food packaging materials, food containers, gypsum board base paper, coated base paper, medium-quality paper, general liners and cores, neutral pure white roll paper, neutral liners, rust-proof liners and metal interleaving paper, kraft paper, neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral heat-sensitive paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper, molded paper (molded containers), etc., and suitable examples include food packaging materials and food containers.

[0188] Substrates that can be treated with the repellent of the present disclosure are not limited to textiles or paper products, but also include stone, filters (e.g., electrostatic filters), dust masks, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster.

[0189] When the substrate is glass, the glass product to be manufactured may be an optical member. The surface (outermost layer) of the glass substrate may have some layer (or film), such as a hard coat layer or an anti-reflection layer. The anti-reflection layer may be either a single-layer anti-reflection layer or a multi-layer anti-reflection layer. Examples of inorganic substances that can be used for the anti-reflection layer include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, CeO2, MgO, Y2O3, SnO2, MgF2, WO3, etc. These inorganic substances may be used alone or in combination of two or more of them (for example, as a mixture). When a multi-layer anti-reflection layer is used, it is preferable to use SiO2 and / or SiO for the outermost layer. When the product to be manufactured is an optical glass part for a touch panel, a transparent electrode, such as a thin film using indium tin oxide (ITO) or indium zinc oxide, may be provided on a part of the surface of the substrate (glass). In addition, the substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomizing film layer, a hard coating film layer, a polarizing film, a phase difference film, and a liquid crystal display module, etc., depending on its specific specifications, etc.

[0190] [Processing method] The repellent of the present disclosure can be applied to a substrate as a treatment agent (particularly a surface treatment agent) by a conventionally known method. The treatment method may be a method in which the repellent of the present disclosure is dispersed and diluted in an organic solvent or water as necessary, and attached to the inside and / or surface of the substrate by a known method such as dip coating, spray coating, foam coating, etc., and then dried. After drying, a product is obtained to which the solid components of the repellent are attached. If necessary, it may be applied together with a suitable crosslinking agent and cured. The repellent of the present disclosure may also be used in combination with various additives such as water and / or oil repellents, slip prevention agents, antistatic agents, texture adjusters, softeners, antibacterial agents, flame retardants, paint fixing agents, anti-wrinkle agents, drying speed adjusters, crosslinking agents, film-forming assistants, compatibilizers, antifreeze agents, viscosity adjusters, ultraviolet absorbers, antioxidants, pH adjusters, insect repellents, and defoamers. Examples of various additives may be the same as those described in the "other components" section above. The concentration of the repellent in the treatment agent to be brought into contact with the substrate may be appropriately changed depending on the application, but may be 0.01 to 10% by weight, for example 0.05 to 5% by weight.

[0191] The repellent can be applied to the substrate by any of the methods known for treating substrates with liquids. The substrate may be immersed in the repellent, or the solution may be applied or sprayed onto the substrate. The treated substrate is preferably dried and cured by heating to develop liquid repellency. The heating temperature may be, for example, 100°C to 200°C, 100°C to 170°C, or 100°C to 120°C. In the present disclosure, good performance can be obtained even with low-temperature heating (for example, 100°C to 140°C). In the present disclosure, the heating time may be 5 seconds to 60 minutes, for example, 30 seconds to 3 minutes. When the textile product is paper, the paper may be coated with the repellent, or the solution may be applied or sprayed onto the paper, or the paper may be mixed with the pulp slurry before papermaking and treated. The treatment may be an external addition treatment or an internal addition treatment. Alternatively, the repellent may be applied to the textile product by a cleaning method, for example, by washing application or dry cleaning method.

[0192] [Processing of paper products] The paper substrate includes paper, paper containers, paper molded articles (e.g., pulp molds), etc. The polyol modified product of the present disclosure can adhere well to the paper substrate.

[0193] The paper can be produced by a conventional papermaking method, either an internal treatment method in which the repellent is added to the pulp slurry before papermaking, or an external treatment method in which the repellent is applied to the paper after papermaking.

[0194] The size press for external additive treatment can be divided into the following types according to the coating method: One application method is a so-called pond-type two-roll size press, in which a coating liquid (size liquid) is supplied to a nip formed by passing paper between two rubber rolls, a coating liquid pool called a pond is created, and the paper is passed through this coating liquid pool to apply the size liquid to both sides of the paper. Other application methods are a gate roll type in which the size liquid is applied by a surface transfer type, and a rod metering size press. In a pond-type two-roll size press, the size liquid is likely to penetrate into the inside of the paper, and in a surface transfer type, the size liquid component is likely to remain on the surface of the paper. In the surface transfer type, the coating layer is more likely to remain on the surface of the paper than in a pond-type two-roll size press, and the coating layer formed on the surface is larger than in a pond-type two-roll size press. In the present disclosure, performance can be imparted to the paper even when the former pond-type two-roll size press is used. The paper thus treated can exhibit excellent oil resistance, water resistance, etc. by optionally accompanying a heat treatment that can take a temperature range of up to 300°C, for example up to 200°C, particularly 80°C to 180°C, depending on the properties of the paper, after simple drying at room temperature or high temperature.

[0195] The internal addition treatment method may mean a treatment method of adding a repellent to a pulp slurry before papermaking. The internal addition treatment method may include, but is not limited to, one or more of the steps of adding a repellent to a pulp slurry and stirring and mixing it, suction-dehydrating the pulp composition prepared in the step through a mesh body of a predetermined shape to deposit the pulp composition to form a pulp mold intermediate, and molding and drying the pulp mold intermediate with a heated mold to obtain paper, a paper container, or a paper molded product. The treated paper may be subjected to a heat treatment depending on the properties of the paper after simple drying at room temperature or at a high temperature. The temperature of the heat treatment may be 150°C or higher, 180°C or higher, or 210°C or higher, and may be 300°C or lower, 250°C or lower, or 200°C or lower, and may be particularly 80°C to 180°C. By performing the heat treatment in such a temperature range, excellent oil resistance and water resistance can be exhibited.

[0196] The present disclosure can be used in gypsum board base paper, coated base paper, medium quality paper, general liners and cores, neutral pure white roll paper, neutral liners, rust-proof liners and metal interleaving paper, kraft paper, etc. It can also be used in neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper, and neutral information paper.

[0197] Pulp raw materials include bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, groundwood pulp, mechanical pulp, or thermomechanical pulp. Any of bleached or unbleached high-yield pulp, recycled newspaper, magazine, corrugated cardboard, deinked recycled paper, etc. may be used. Mixtures of the above pulp raw materials with synthetic fibers such as asbestos, polyamide, polyimide, polyester, polyolefin, polyvinyl alcohol, etc. may also be used.

[0198] The water resistance of paper can be improved by adding a sizing agent. Examples of the sizing agent include cationic sizing agents, anionic sizing agents, and rosin-based sizing agents (e.g., acidic rosin-based sizing agents, neutral rosin-based sizing agents). The amount of the sizing agent may be 0.01 to 5% by weight based on the pulp.

[0199] If necessary, the paper may contain additives used in the manufacture of paper, such as paper strength enhancers such as starch, modified starch, carboxymethyl cellulose, and polyamide polyamine-epichlorohydrin resin, flocculants, fixing agents, retention improvers, dyes, fluorescent dyes, slime control agents, and defoamers, to the extent that they are commonly used. Starch and modified starch are preferably used. If necessary, repellents can be applied to the paper using starch, polyvinyl alcohol, dyes, coating colors, anti-slip agents, and the like, by a size press, gate roll coater, bill blade coater, calendar, or the like.

[0200] In the case of external addition, the amount of the polyol modifier contained in the coating layer is 0.01 to 2.0 g / m 2 , especially 0.1 to 1.0 g / m 2 The coating layer is preferably formed from a repellent and starch and / or modified starch. The solid content of the paper repellent in the coating layer is preferably 2 g / m 2 It is preferable that: In the case of internal addition, it is preferable to mix the repellent with the pulp so that the amount of the repellent is 0.01 to 50 parts by weight or 0.01 to 30 parts by weight, for example 0.01 to 10 parts by weight, and particularly 0.2 to 5.0 parts by weight, per 100 parts by weight of the pulp forming the paper.

[0201] In the case of external addition, oil resistance can also be imparted to paper by using a so-called pond-type two-roll size press process in which the treatment solution is pooled between rolls and the base paper is passed through the treatment solution between the rolls at any roll speed and nip pressure.

[0202] In the external addition treatment, the paper substrate may contain additives such as sizing agents, paper strength agents, flocculants, retention agents or coagulants. The additives may be nonionic, cationic, anionic or amphoteric. The ionic charge density of the additives may be -10000 to 10000 μeq / g, preferably -4000 to 8000 μeq / g, more preferably -1000 to 7000 μeq / g. Additives such as sizing agents, paper strength agents, flocculants, retention agents or coagulants (solids or active ingredients) can generally be used in an amount of 0.1 to 10% by weight (e.g., 0.2 to 5.0% by weight) based on the pulp. In the case of a paper substrate containing a cationic additive (e.g., sizing agents, paper strength agents, flocculants, retention agents or coagulants), the repellent is preferably anionic.

[0203] In the internal addition treatment, it is preferable to make a pulp slurry having a pulp concentration of 0.5 to 5.0% by weight (e.g., 2.5 to 4.0% by weight).Additives (e.g., sizing agents, paper strength agents, flocculants, retention agents, coagulants, etc.) and polyol modifiers can be added to the pulp slurry. Examples of additives (e.g., sizing agents, paper strength agents, flocculants, retention agents, or coagulants) include alkylketene dimers, alkenyl succinic anhydrides, styrene polymers (styrene / maleic acid polymers, styrene / acrylic acid polymers), urea-formaldehyde polymers, polyethyleneimine, melamine-formaldehyde polymers, polyamidoamine-epichlorohydrin polymers, polyacrylamide polymers, polyamine polymers, polydiallyldimethylammonium chloride, alkylamine-epichlorohydrin condensates, condensates of alkylene dichlorides and polyalkylenepolyamines, dicyandiamide-formaldehyde condensates, dimethyldiallylammonium chloride polymers, and olefin / maleic anhydride polymers.

[0204] [Pretreatment of textile products] The textile product may be pretreated before being treated with the repellent of the present disclosure. Pretreatment of the textile product may impart excellent fastness to the textile product after treatment with the repellent.

[0205] Examples of pretreatments of textile products include cationization treatment by reaction with a reactive quaternary ammonium salt, anionization treatment such as sulfonation, carboxylation, and phosphation, and acetylation treatment, benzoylation treatment, carboxymethylation treatment, grafting treatment, tannic acid treatment, and polymer coating treatment after anionization treatment.

[0206] The method for pretreating a textile product is not limited, and the textile product can be pretreated by a conventionally known method. The pretreatment liquid may be dispersed and diluted in an organic solvent or water as necessary, and applied to the inside and / or surface of the textile product by a known method such as dip coating, spray coating, foam coating, etc., and then dried. The pH and temperature of the pretreatment liquid may be adjusted depending on the desired degree of treatment. As an example of the method for pretreating a textile product, a method for pretreating a textile product with the above-mentioned treatment agent will be described in detail.

[0207] The pretreatment method for textile products is to add -SO3M to the fibers. 1 (In the formula, M 1 represents a monovalent cation), -COOM 2 (In the formula, M 2 represents a monovalent cation), and -OP(O)(OX 1 )(OX 2 )(wherein, X 1 and X 2 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms) (hereinafter, also referred to as "specific functional groups").

[0208] M 1 Examples of M include H, K, Na, and ammonium ion which may have a substituent. 2 Examples of X include H, K, Na, and ammonium ion which may have a substituent. 1 Or X 2 When is an alkyl group, it is preferably an alkyl group having 1 to 22 carbon atoms, and more preferably an alkyl group having 4 to 12 carbon atoms.

[0209] The fibers containing the specific functional groups (hereinafter, sometimes referred to as "functional group-containing fibers") can be prepared, for example, by the following method. (i) A compound having the specific functional group is attached to a fiber material. The attachment of the compound may be in a state where a part of the compound is chemically bonded to a part of the fiber to the extent that a sufficient amount of the specific functional group remains. (ii) A fiber is prepared in which the specific functional group is directly introduced into the material constituting the fiber.

[0210] In the case of (i), for example, a functional group-containing fiber can be obtained by a functional group introduction step in which a fiber material is treated with a pretreatment liquid containing one or more compounds having the specific functional group.

[0211] The material of the fiber material is not particularly limited, and examples thereof include natural fibers such as cotton, hemp, silk, wool, etc., semi-synthetic fibers such as rayon, acetate, etc., synthetic fibers such as polyamide (nylon, etc.), polyester, polyurethane, polypropylene, etc., and composite fibers, blended fibers, etc. The form of the fiber material may be any of fibers (tow, sliver, etc.), yarn, knitted fabric (including interwoven fabric), woven fabric (including interwoven fabric), nonwoven fabric, etc.

[0212] In this embodiment, from the viewpoint of improving the water repellency of the obtained textile product, it is preferable to use textile materials containing polyamide and polyester as raw materials, and in particular, it is preferable to use nylons such as nylon 6 and nylon 6,6, polyesters such as polyethylene terephthalate (PET), polytrimethyl terephthalate, and polylactic acid, and mixed fibers containing these.

[0213] Above -SO3M 1 As the compound having the formula (I), a phenol-based polymer can be used. As such a phenol-based polymer, for example, one containing at least one compound represented by the following general formula can be mentioned.

[0214] TIFF2025066772000001.tif4678 [In the formula, X 2 Ha-SO3M 3 (In the formula, M 3 represents a monovalent cation) or a group represented by the following general formula, and n is an integer of 20 to 3000.

[0215] TIFF2025066772000002.tif2661 [In the formula, M 4 represents a monovalent cation.

[0216] The above M 3 Examples of the cation include H, K, Na, and ammonium ion which may have a substituent.

[0217] The above M 4 Examples of the cation include H, K, Na, and ammonium ion which may have a substituent.

[0218] The compound represented by the above general formula may be, for example, a formalin condensate of phenolsulfonic acid or a formalin condensate of sulfonated bisphenol S.

[0219] Above - COOM 2 Examples of compounds having the formula include polycarboxylic acid polymers.

[0220] As the polycarboxylic acid polymer, for example, a polymer synthesized by a conventionally known radical polymerization method using acrylic acid, methacrylic acid, maleic acid, or the like as a monomer, or a commercially available product can be used.

[0221] Examples of the method for producing a polycarboxylic acid polymer include a method in which a radical polymerization initiator is added to an aqueous solution of the above-mentioned monomer and / or its salt, and the mixture is heated and reacted at 30 to 150° C. for 2 to 5 hours. At this time, an alcohol such as methanol, ethanol, isopropyl alcohol, or an aqueous solvent such as acetone may be added to the aqueous solution of the above-mentioned monomer and / or its salt. Examples of the radical polymerization initiator include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, redox-based polymerization initiators such as combinations of persulfates and sodium bisulfite, hydrogen peroxide, and water-soluble azo-based polymerization initiators. These radical polymerization initiators may be used alone or in combination of two or more. Furthermore, during radical polymerization, a chain transfer agent (e.g., octyl thioglycolate) may be added for the purpose of adjusting the degree of polymerization.

[0222] In addition to the above monomers, copolymerizable monomers can be used in the radical polymerization. Examples of the copolymerizable monomers include vinyl monomers such as ethylene, vinyl chloride, and vinyl acetate, acrylamide, acrylates, and methacrylates. The acrylates and methacrylates are preferably those having a hydrocarbon group having 1 to 3 carbon atoms which may have a substituent such as a hydroxyl group. Examples of such acrylates or methacrylates include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, propyl acrylate, and propyl methacrylate. These copolymerizable monomers may be used alone or in combination of two or more.

[0223] The carboxyl group in the polycarboxylic acid polymer may be free or may be neutralized with an alkali metal, an amine compound, etc. Examples of the alkali metal include sodium, potassium, and lithium, and examples of the amine compound include ammonia, monoethanolamine, diethanolamine, and triethanolamine.

[0224] The weight average molecular weight of the polycarboxylic acid polymer is preferably from 1,000 to 20,000, and more preferably from 3,000 to 15,000, from the viewpoint of improving the water repellency of the resulting textile product.

[0225] As the polycarboxylic acid polymer, commercially available products such as "Neocrystal 770" (product name, manufactured by Nicca Chemical Co., Ltd.) and "Ceropol PC-300" (product name, manufactured by Sanyo Chemical Industries, Ltd.) can be used.

[0226] Above -OP(O)(OX 1 )(OX 2 ) is exemplified by a phosphate ester compound represented by the following general formula: TIFF2025066772000003.tif3243[where, X 1 Or X 2 is the same as above, and X 3 represents an alkyl group having 1 to 22 carbon atoms.

[0227] As the phosphate ester compound, phosphate monoesters, diesters and triesters, in which the alkyl ester moiety is an alkyl group having 1 to 22 carbon atoms, and mixtures thereof can be used.

[0228] From the viewpoint of improving the water repellency of the resulting textile product, it is preferable to use lauryl phosphate and decyl phosphate.

[0229] As the phosphate ester compound, for example, a commercially available product such as "Phosphanol ML-200" (product name, manufactured by Toho Chemical Industry Co., Ltd.) can be used.

[0230] The pretreatment liquid containing one or more compounds having the specific functional group may be, for example, an aqueous solution of the above-mentioned compounds. The pretreatment liquid may also contain an acid, an alkali, a surfactant, a chelating agent, etc.

[0231] Examples of the method for treating the textile material with the pretreatment liquid include padding, immersion, spraying, and coating. Examples of padding include a method using a padding device described on pages 396-397 of Textile Dyeing and Processing Dictionary (published by Nikkan Kogyo Shimbun, 1963) and pages 256-260 of Color Dyeing Chemistry III (published by Jikkyo Publishing Co., Ltd., 1975). Examples of coating include a method using a coating machine described on pages 473-477 of Dyeing and Finishing Equipment Directory (published by Sen-sha, 1981). Examples of immersion include a method using a batch-type dyeing machine described on pages 196-247 of Dyeing and Finishing Equipment Directory (published by Sen-sha, 1981), and a liquid flow dyeing machine, air flow dyeing machine, drum dyeing machine, winch dyeing machine, washer dyeing machine, cheese dyeing machine, etc. can be used. Examples of the spray treatment include an air spray in which the treatment liquid is sprayed in the form of a mist using compressed air, and a method using an air spray of a liquid pressure atomization type. The treatment conditions, such as the concentration of the treatment liquid and the heat treatment after application, can be appropriately adjusted in consideration of various conditions such as the purpose and performance. In addition, when the pretreatment liquid contains water, it is preferable to dry the pretreatment liquid after it is applied to the fiber material in order to remove the water. There is no particular limit to the drying method, and either a dry heat method or a wet heat method may be used. There is also no particular limit to the drying temperature, and for example, drying may be performed at room temperature to 200°C for 10 seconds to several days. If necessary, heat treatment may be performed at a temperature of 100 to 180°C for about 10 seconds to 5 minutes after drying.

[0232] When the textile material is to be dyed, the treatment with the pretreatment liquid may be carried out before dyeing or in the same bath as the dyeing. However, when reduction soaping is carried out, there is a risk that the compound having the specific functional group (e.g., a phenolic polymer compound, etc.) adsorbed during the process may fall off, so it is preferable to carry out the treatment after reduction soaping after dyeing.

[0233] The treatment temperature in the immersion treatment can be 60 to 130° C. The treatment time can be 5 to 60 minutes.

[0234] In the functional group introduction step using a pretreatment liquid, the amount of the compound having the specific functional group attached is preferably 1.0 to 7.0 parts by weight per 100 parts by weight of the textile material. Within this range, durable water repellency and texture can be simultaneously achieved at high levels.

[0235] The pretreatment liquid is preferably adjusted to a pH of 3 to 5. The pH can be adjusted using a pH adjuster such as acetic acid or malic acid.

[0236] In the pretreatment solution, a salt may be used in combination in order to effectively adsorb the compound having the specific functional group to the fiber material by the salting-out effect. Examples of the salt that can be used include sodium chloride. Examples of suitable salts include sodium carbonate, ammonium sulfate, and sodium sulfate.

[0237] In the functional group introduction step using the pretreatment liquid, it is preferable to remove the compound having the specific functional group that has been treated in excess. An example of a removal method is washing with water. By removing the compound sufficiently, it is possible to prevent the development of water repellency in the subsequent water repellent treatment from being hindered, and in addition, the texture of the obtained textile product is improved. In addition, it is preferable to thoroughly dry the obtained functional group-containing fiber before contacting it with the above-mentioned treatment agent.

[0238] (ii) An example of a fiber in which the specific functional group is directly introduced into the material constituting the fiber is cationic dyeable polyester (CD-PET).

[0239] From the viewpoint of improving the water repellency of the resulting textile product, the functional group-containing fiber preferably has a surface zeta potential of −100 to −0.1 mV, more preferably −50 to −1 mV. The zeta potential of the fiber surface can be measured, for example, by a zeta potential / particle size measuring system ELSZ-1000ZS (manufactured by Otsuka Electronics Co., Ltd.).

[0240] Although the embodiments have been described above, it will be understood that various changes in form and details are possible without departing from the spirit and scope of the claims. EXAMPLES

[0241] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to these examples.

[0242] <Test Method> The test procedure is as follows.

[0243] [Volume ratio of particles 100 μm or larger] The frequency distribution of the water-dispersed repellent was obtained by measuring it with a laser diffraction / scattering device, and the amount of particles with a size of 100 μm or more was divided by the amount of all particles present to calculate the ratio. Specifically, the calculation was performed using the following formula.

[0244] Volumetric abundance ratio of particles 100 μm or larger = [abundance of particles 100 μm or larger / abundance of all particles] * 100

[0245] [Median diameter D50] The repellency of the water-dispersed agent was determined by measurement using a laser diffraction / scattering device.

[0246] [Differential scanning calorimetry of modified polyols] The maximum endothermic peak temperature, melting point, crystallization temperature, and glass transition temperature of the polyol modified product were calculated by differential scanning calorimetry (DSC). DSC measurements were performed in a nitrogen atmosphere, with the sample cooled to -20°C, and the endothermic peak observed during the subsequent heating process to 180°C at 10°C / min was measured. When multiple melting peaks appeared, the peak with the largest amount of endothermic heat was taken as the maximum endothermic peak, and the top of this peak was taken as the maximum endothermic peak temperature. The amount of endothermic heat was calculated by calculating the amount of heat within a range of ±10°C of the endothermic peak temperature.

[0247] [Differential scanning calorimetry of the solid component obtained by removing the liquid medium from the repellent] The maximum endothermic peak temperature, melting point, crystallization temperature, and glass transition temperature of the solid component obtained by removing the liquid medium from the repellent were calculated by differential scanning calorimetry (DSC). The liquid medium was removed from the repellent by drying it at 150°C for 1 hour. DSC measurements were performed under a nitrogen atmosphere, with the sample cooled to -20°C, and endothermic peaks observed during the subsequent heating process to 180°C at 10°C / min were measured. When multiple endothermic peaks appeared, the highest endothermic peak was taken as the maximum endothermic peak, and the top of this peak was taken as the maximum endothermic peak temperature. The endothermic heat was calculated by calculating the heat within a range of ±10°C of the endothermic peak temperature.

[0248] [Variable temperature X-ray diffraction measurement of the solid component obtained by removing the liquid medium from the repellent] The crystal state of the solid component obtained by removing the liquid medium from the repellent was measured by X-ray diffraction (XRD) using RIGAKU's SmartLab. Cu Kα radiation was used as the light source. Variable temperature XRD (XRD-DSC) measurements were performed in a nitrogen atmosphere, after cooling to -20°C, heating to 25°C or 55°C at 5°C / min, and holding for 5 minutes before measurement. The half-width of a peak was defined as the 2θ width of the peak at half the intensity between the baseline and the peak top. Diffraction intensity ratio [A 55℃ / A 25℃ ] was calculated as follows: The intensity of the maximum point of the diffraction intensity in the 2θ range of 15° to 30° at a measurement temperature of 25°C is [Peak Intensity A 25℃ The intensity of the maximum point of the diffraction intensity in the region of 2θ from 15° to 30° at a measurement temperature of 55°C was [Peak Intensity A 55℃ ] was calculated as follows: 55℃ ] to [Peak Intensity A 25℃ ] to obtain the diffraction intensity ratio [A 55℃ / A 25℃ ] was calculated. Diffraction intensity ratio [A 55℃ / A 25℃ ]=[Peak Intensity A 55℃ ] / [Peak Intensity A 25℃ ] The liquid medium was removed from the repellent by drying at 150°C for 1 hour.

[0249] [HD contact angle] A solution (or dispersion) of the polyol-modified compound with a solid content concentration of 1.0% was spin-coated on a silicon wafer at 2500 rpm for 25 seconds to obtain a spin-coated film. This was then heated at 140°C for 1 minute to produce a silicon wafer treated with the polyol-modified compound. Chloroform was used as the solvent or dispersion medium. 2 μL of HD (hexadecane) was dropped onto the polyol-modified silicon wafer, and the contact angle 1 second after the drop landed was taken as the HD contact angle of the polyol-modified compound.

[0250] [Water contact angle] A solution (or dispersion) of the polyol-modified product with a solid content concentration of 1.0% was spin-coated on a silicon wafer at 2500 rpm for 25 seconds to obtain a spin-coated film. This was heated at 140°C for 1 minute to produce a silicon wafer treated with the polyol-modified product. Chloroform was used as the solvent or dispersion medium. 2 μL of water was dropped onto the polyol-modified silicon wafer, and the contact angle 1 second after the drop landed was taken as the water contact angle of the polyol-modified product.

[0251] [Making pulp molds] Pulp mold was formed using an automatic molding machine. A mesh-like body was placed on a metal pulp mold mold with many suction holes at the bottom, and a metal tank was placed at the top, with a mixture of pulp slurry and water-dispersed repellent being placed in the upper metal tank. The pulp-containing aqueous composition was sucked and dehydrated through the pulp mold mold and mesh-like body by a vacuum pump from the side opposite to the side where the mesh-like body was placed in the pulp mold mold, and the solid content (pulp, etc.) contained in the pulp-containing aqueous composition was deposited on the mesh-like body to obtain a pulp mold intermediate. Next, the obtained pulp mold intermediate was dried under a pressure of 0.05 to 5 MPa from above and below in a male-female metal mold heated to 60 to 250°C. This produced a pulp molded product molded into the shape of a container.

[0252] [65℃ oil resistance test] 100 ml of corn oil at 65°C was poured into the pulp mold, and after leaving it at room temperature for 45 minutes, the corn oil was removed from the pulp mold and the degree of soaking into the pulp mold was evaluated. The following evaluation values ​​were set according to the degree of soaking. 5: No stains on the inside 4: Stain on the inside. No stain on the back. 3: Stain on the inside. Slight seepage on the back. 2: Stain on the inside. Less than 50% of the area has seeped through to the back. 1: Stain on the inside. Stain on the back is 50% or more but less than 100% of the area. 0: Seeping through to the entire back side.

[0253] [Room temperature oil resistance test] 100 ml of corn oil at 25°C was poured into the pulp mold, and after leaving it at room temperature for 45 minutes, the corn oil was removed from the pulp mold and the degree of soaking into the pulp mold was evaluated. The following evaluation values ​​were set according to the degree of soaking. 5: No stains on the inside 4: Stain on the inside. No stain on the back. 3: Stain on the inside. Slight seepage on the back. 2: Stain on the inside. Less than 50% of the area has seeped through to the back. 1: Stain on the inside. Stain on the back is 50% or more but less than 100% of the area. 0: Seeping through to the entire back side.

[0254] [65℃ water resistance test] 100 ml of water at 65°C was poured into the pulp mold, and after leaving it at room temperature for 45 minutes, the water was removed from the pulp mold and the degree of soaking into the pulp mold was evaluated. The following evaluation values ​​were set according to the degree of soaking. 5: No stains on the inside 4: Stain on the inside. No stain on the back. 3: Stain on the inside. Slight seepage on the back. 2: Stain on the inside. Less than 50% of the area has seeped through to the back. 1: Stain on the inside. Stain on the back is 50% or more but less than 100% of the area. 0: Seeping through to the entire back side.

[0255] [Room temperature water resistance test] 100 ml of water at 25°C was poured into the pulp mold, and after leaving it at room temperature for 45 minutes, the water was removed from the pulp mold and the degree of soaking into the pulp mold was evaluated. The following evaluation values ​​were set according to the degree of soaking. 5: No stains on the inside 4: Stain on the inside. No stain on the back. 3: Stain on the inside. Slight seepage on the back. 2: Stain on the inside. Less than 50% of the area has seeped through to the back. 1: Stain on the inside. Stain on the back is 50% or more but less than 100% of the area. 0: Seeping through to the entire back side.

[0256] [Preparation of treated paper] A pulp slurry was prepared with a weight ratio of 60% LBKP (hardwood bleached kraft pulp) and 40% NBKP (softwood bleached kraft pulp) as wood pulp, and with a pulp freeness of 400 ml (Canadian Standard Freeness). A wet strength agent and a sizing agent were added to the pulp slurry, and the paper was spun on a fourdrinier paper machine to a paper density of 0.58 g / cm. 3 Grammage: 45g / m 2 The paper was used as the base paper for external treatment (size press treatment). The oil resistance (KIT value) of this base paper was 0, and the water resistance (Cobb value) was 52 g / m 2 It was. A treatment solution in which the compound was dissolved in chloroform at a ratio of 14.9 mg / mL was applied to this base paper using a Baker-type applicator with a gap set to 0 mil and dried three times, and then dried at 140°C for one minute to produce treated paper.

[0257] [KIT test (oil resistance)] Measurements were made using the 3M Kit Test (TAPPI T-559cm-02). The 3M Kit Test method involves placing a test oil containing castor oil, toluene, and heptane on the surface of treated paper, wiping the test oil off after 15 seconds, and evaluating the presence or absence of oil stains on the treated paper. Tests were performed using test oils with kit numbers 1 to 6, and the highest kit number that showed no stains was used to evaluate the oil resistance.

[0258] [Corn oil resistance test (oil resistance)] Corn oil is placed on the surface of the treated paper, and after 15 seconds the test oil is wiped off. The evaluation is based on whether or not the treated paper is stained with oil. If there is no stain, mark it as a circle; if there is a stain, mark it as an X.

[0259] [HD contact angle measurement and differential scanning calorimetry of polyol modified bodies] Table 1 shows the results of HD contact angle measurement and differential scanning calorimetry (DSC) for the following modified polyols: decaglycerol dodecabehenyl ester (degree of polymerization 10, hydroxyl group substitution rate: 12 / 12*100, biobased ratio: 100%), decaglycerol heptabehenyl ester (degree of polymerization 10, hydroxyl group substitution rate: 7 / 12*100), decaglycerol decastearyl ester (degree of polymerization 10, hydroxyl group substitution rate: 10 / 12*100), hexaglycerol pentastearyl ester (degree of polymerization 6, hydroxyl group substitution rate: 5 / 8*100), and tetraglycerol tristearyl ester (degree of polymerization 4, hydroxyl group substitution rate: 3 / 6*100).

[0260] Example 1 2g of decaglycerol dodecabehenyl ester (polymerization degree 10, hydroxyl group substitution rate: 12 / 12*100, bio-based ratio: 100%) as a polyol modification, 0.2g of polyethylene oxide alkyl ether (alkyl carbon number 6-16 HLB: 7), and 17.8g of water were mixed to obtain a precursor A of a water-dispersed repellent. This precursor A of a water-dispersed repellent was heated to 80°C, and then cooled while stirring with a magnetic stirrer to obtain a precursor B of a water-dispersed repellent. The precursor B of a water-dispersed repellent was treated twice under a condition of 100 MPa in a high-pressure wet microparticulation device to obtain a water-dispersed repellent. The volumetric ratio of particles of 100 μm or more in the obtained water-dispersed repellent was 0%, and the median diameter D50 was 6.1 μm. The solid component obtained by removing the liquid medium from the water-dispersed repellent was subjected to differential scanning calorimetry and variable temperature X-ray diffraction measurement, and the results are shown in Table 1. The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt % so that the ratio of the aqueous dispersion composition to the pulp was 3.5 wt % in terms of solid content, to prepare a pulp composition. The pulp composition was placed in an automatic molding machine to prepare a pulp mold. The pulp mold was subjected to an oil resistance test at 65°C and a water resistance test at 65°C, and the oil resistance was 4 points and the water resistance was 4 points. The results are shown in Table 1. In addition, oil resistance and water resistance tests at room temperature were also conducted, and the results are shown in Table 1.

[0261] Example 2 2g of decaglycerol dodecabehenyl ester (polymerization degree 10, hydroxyl group substitution rate: 12 / 12*100, bio-based ratio: 100%) as a polyol modification, 0.2g of polyethylene oxide trimethyl nonyl ether (HLB: 13), and 17.8g of water were mixed to obtain a precursor A of a water-dispersed repellent. This precursor A of a water-dispersed repellent was heated to 80°C, and then stirred at 7000 rpm for 20 minutes with a homogenizer to obtain a water-dispersed repellent. The volumetric abundance ratio and median diameter D50 of particles of 100 μm or more of the obtained water-dispersed repellent, as well as the results of differential scanning calorimetry and variable temperature X-ray diffraction measurement of the solid component obtained by removing the liquid medium from the water-dispersed repellent, are shown in Table 1. As in Example 1, an oil resistance test at 65°C and a water resistance test at 65°C were conducted, and the oil resistance was 4 points and the water resistance was 4 points. The results are shown in Table 1. In addition, a room temperature oil resistance test and a room temperature water resistance test were also conducted, and the results are shown in Table 1.

[0262] Example 3 2 g of decaglycerol heptabehenyl ester (polymerization degree 10, hydroxyl group substitution rate: 7 / 12*100, bio-based ratio: 100%) as a polyol modification product, 0.2 g of polyethylene oxide trimethyl nonyl ether, and 17.8 g of water were mixed to obtain a precursor A of a water-dispersed repellent. This precursor A of a water-dispersed repellent was heated to 80°C, and then stirred at 7000 rpm for 20 minutes with a homogenizer to obtain a water-dispersed repellent. The volumetric abundance ratio and median diameter D50 of particles of 100 μm or more of the obtained water-dispersed repellent, as well as the results of differential scanning calorimetry and variable temperature X-ray diffraction measurement of the solid component obtained by removing the liquid medium from the water-dispersed repellent, are shown in Table 1. The aqueous dispersion composition was added to a pulp slurry having a concentration of 0.5 wt % so that the ratio of the aqueous dispersion composition to the pulp was 5 wt % in terms of solid content, to prepare a pulp composition. The pulp composition was placed in an automatic molding machine to prepare a pulp mold. The pulp mold was subjected to an oil resistance test at 65°C and a water resistance test at 65°C, and the oil resistance was scored at 4 points and the water resistance was scored at 4 points. In addition, oil resistance and water resistance tests at room temperature were also conducted, and the results are shown in Table 1.

[0263] Example 4 A water-dispersed repellent was obtained by the same procedure as in Example 2, except that polyethylene oxide alkyl ether was replaced with benzalkonium chloride. The volume ratio of particles of 100 μm or more and the median diameter D50 of the obtained water-dispersed repellent were 1% and 7.7 μm. As in Example 1, the oil resistance test at 65° C. and the water resistance test at 65° C. were performed, and the oil resistance was 4 points and the water resistance was 4 points.

[0264] Example 5 A water-dispersed repellent was obtained in the same manner as in Example 1. A pulp slurry was prepared using wood pulp with a weight ratio of 60% by weight (LBKP) and 40% by weight (NBKP), and the pulp had a freeness of 400 ml (Canadian Standard Freeness). A wet strength agent and a sizing agent were added to the pulp slurry, and the slurry was spun on a Fourdrinier paper machine to a paper density of 0.58 g / cm. 3 Grammage: 45g / m 2 The paper was used as the base paper for external treatment (size press treatment). The oil resistance (KIT value) of this base paper was 0, and the water resistance (Cobb value) was 52 g / m 2 It was. A treatment solution in which the compound was dissolved in chloroform at a ratio of 14.9 mg / mL was applied to this base paper using a Baker-type applicator with a gap set to 7 mil, and the drying process was repeated three times, and the paper was then dried at 140°C for 5 minutes to produce treated paper. The corn oil resistance of the treated paper was rated as "good" and the KIT score was 4 points.

[0265] Example 6 A water-dispersible repellent was obtained in the same manner as in Example 1. 2.5 g of cationic starch was mixed with 47.5 g of water and stirred at 60° C. for 1 hour to prepare an aqueous cationic starch solution. A water-dispersed repellent was added to a pulp slurry with a concentration of 0.5 wt% so that the ratio of the repellent to the pulp was 3.5 wt% in terms of solid content, and then a cationic starch aqueous solution was added so that the ratio of the cationic starch to the pulp was 10 wt% in terms of solid content, to prepare a pulp composition. The pulp composition was placed in an automatic molding machine to produce a pulp mold. The pulp mold was subjected to a room temperature oil resistance test and scored 4 points.

[0266] Comparative Example 1 2 g of decaglycerol decastearyl ester (polymerization degree 10, hydroxyl group substitution rate: 10 / 12*100) as a polyol modification, 0.2 g of polyethylene oxide trimethyl nonyl ether, and 17.8 g of water were mixed to obtain a precursor A of a water-dispersed repellent. This precursor A of a water-dispersed repellent was heated to 80°C, and then stirred at 7000 rpm for 20 minutes with a homogenizer to obtain a water-dispersed repellent. The volumetric abundance ratio and median diameter D50 of particles of 100 μm or more of the obtained water-dispersed repellent, as well as the results of differential scanning calorimetry and variable temperature X-ray diffraction measurement of the solid component obtained by removing the liquid medium from the water-dispersed repellent, are shown in Table 1. As in Example 3, an oil resistance test at 65° C. and a water resistance test at 65° C. were performed, and the oil resistance and water resistance were both scored at 0 points.

[0267] Comparative Example 2 Except for changing the polyol modifier to hexaglycerol pentastearyl ester (degree of polymerization 6, hydroxyl group substitution rate: 5 / 8*100), a water-dispersible repellent was obtained in the same manner as in Comparative Example 1. Table 1 shows the results of differential scanning calorimetry and variable temperature X-ray diffraction measurement of the solid component obtained by removing the liquid medium from the water-dispersible repellent, as well as the volumetric abundance ratio and median diameter D50 of particles of 100 μm or more in the obtained water-dispersible repellent. As in Example 3, an oil resistance test at 65° C. and a water resistance test at 65° C. were performed, and the oil resistance and water resistance were both scored at 0 points.

[0268] Comparative Example 3 Except for changing the polyol modifier to tetraglycerol tristearyl ester (degree of polymerization 4, hydroxyl group substitution rate: 3 / 6*100), a water-dispersible repellent was obtained in the same manner as in Comparative Example 1. The volumetric abundance ratio and median diameter D50 of particles of 100 μm or more in the obtained water-dispersible repellent, as well as the results of differential scanning calorimetry and variable temperature X-ray diffraction measurement of the solid component obtained by removing the liquid medium from the water-dispersible repellent are shown in Table 1. As in Example 3, an oil resistance test at 65° C. and a water resistance test at 65° C. were performed, and the oil resistance and water resistance were both scored at 0 points.

[0269] Comparative Example 4 Except for changing to glycerin tristearyl ester (degree of polymerization 1, hydroxyl group substitution rate: 3 / 3*100), a water-dispersed repellent was obtained in the same manner as in Comparative Example 1. The volumetric abundance ratio and median diameter D50 of particles of 100 μm or more in the obtained water-dispersed repellent, as well as the results of differential scanning calorimetry and variable temperature X-ray diffraction measurement of the solid component obtained by removing the liquid medium from the water-dispersed repellent are shown in Table 1. As in Example 3, an oil resistance test at 65° C. and a water resistance test at 65° C. were performed, and the oil resistance and water resistance were both scored at 0 points.

[0270] [Table 1]

Claims

1. A water-dispersible repellent comprising a modified polyol and a dispersant, A repellent that satisfies one or more of (1) and (2). (1) In a differential scanning calorimetry measurement of the polyol modified product, or in a differential scanning calorimetry measurement of a solid component obtained by removing the liquid medium from the repellent, the temperature of the maximum endothermic peak in the temperature range of 25°C to 180°C is 55°C or higher. (2) The modified polyol has four or more monovalent hydrocarbon groups having 20 to 40 carbon atoms, each of which may have a substituent.

2. The repellent according to claim 1, wherein the polyol modified product has a maximum endothermic peak temperature of 55°C or higher in a temperature range of 25°C to 180°C in differential scanning calorimetry.

3. The repellent according to claim 1, wherein, in differential scanning calorimetry of a solid component obtained by removing the liquid medium from the repellent, the temperature of a maximum endothermic peak in a temperature range of 25°C to 180°C is 55°C or higher.

4. The peak intensity A of the maximum peak at a measurement temperature of 25° C. in the range of 2θ of 15° to 30° measured by variable temperature X-ray diffraction method of the solid component obtained by removing the liquid medium from the repellent agent ２５℃ and the peak intensity A of the maximum peak at the measurement temperature of 55 °C ５５℃ Diffraction intensity ratio [A ５５℃ / A ２５℃ 2. The repellent according to claim 1, wherein the value of is 0.5 or more.

5. The repellent according to claim 1 , wherein the modified polyol has four or more optionally substituted monovalent hydrocarbon groups having from 20 to 40 carbon atoms.

6. The repellent according to claim 5 , wherein the monovalent hydrocarbon group having from 20 to 40 carbon atoms which may have a substituent is an alkyl group.

7. The polyol modification modifies four or more hydroxy groups of the polyol to the following formula: -Y-Z ｎ [In the formula, Y is Y １ and Y ２ is a 1+n valent group consisting of one or more selected from the group consisting of Y １ is a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O) ２ -, -NR'-, -C(OR')R'-, and -C(OR')(-) ２ , -N(-) ２ (wherein R' is independently at each occurrence a hydrogen atom or an organic group having 1 to 30 carbon atoms); Y ２ is a group consisting of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent aromatic hydrocarbon rings, and optionally substituted di- to tetravalent heterocycles, Z is a monovalent hydrocarbon group having 20 to 40 carbon atoms which may have a substituent, n is an integer of 1 to 3. The repellent according to claim 1, which is a compound substituted with a group represented by the following formula:

8. Y -O-Y １１ - or -O-Y １１ -Y ２１ -Y １２ - wherein each symbol represents independently at each occurrence: Y １１ is a direct bond, -C(=O)-, -C(=O)-NR'-, or -C(=S)-NR'-; Y ２１ is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, Y １２ が-O-、-O-C(=O)-、-O-C(=O)-O-、-C(=O)-NR-、-O-C(=O)-OR-、-O-C(=O)-O-、--O--- O)-、-NR'-C(=O)-O-、-NR’-C(=O)-NR’-、-C(=O)-、-C(=O)-O-、-C(=O)-[O---- ２ -、-S ２ NR'-、-C(OR')(-) ２ かる。]、 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 hydroxy group-containing compound polymers.

10. The polyol is Glucose, fructose, galactose, xylose; Sucrose, cycloamylose, cyclodextrin, maltose, trehalose, lactose, sucralose; Sorbitol, maltitol, erythritol, isomalt, lactitol, mannitol, xylitol, sorbitan, lactitol; Starch, cellulose, curdlan, pullulan, alginic acid, carrageenan, guar gum, chitin, chitosan, locust bean gum, kappa carrageenan, iota carrageenan, isomaltodextrin, gellan gum, tamarind seed gum; Ascorbic acid, kojic acid, quinic acid, chlorogenic acid, gluconic acid; Glucosamine; Inositol; Catechins, quercetin, anthocyanins; Ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, glycerol, 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 polymers, hydroxypropyl (meth)acrylate polymers, and hydroxybutyl (meth)acrylate polymers.

11. 2. The repellent according to claim 1, wherein the volumetric ratio of particles having a size of 100 μm or more is 25% or less as measured by a laser diffraction scattering method.

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

13. The polyol modification is achieved by modifying the hydroxy group of the polyol with the formula: -Y-Z ｎ [In the formula, Y -O-Y １１ - or -O-Y １１ -Y ２１ -Y １２ - wherein each symbol represents independently at each occurrence: Y １１ is a direct bond, -C(=O)-, -C(=O)-NR'-, or -C(=S)-NR'-; Y ２１ is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, Y １２ が-O-、-O-C(=O)-、-O-C(=O)-O-、-C(=O)-NR-、-O-C(=O)-OR-、-O-C(=O)-O-、--O--- O)-、-NR'-C(=O)-O-、-NR’-C(=O)-NR’-、-C(=O)-、-C(=O)-O-、-C(=O)-[O---- ２ -、-S ２ NR'-、-C(OR')(-) ２ かる。] and Z is a hydrocarbon group having 6 to 40 carbon atoms, n is an integer of 1 to 3. is a compound substituted with a group represented by The polyol is Glucose, fructose, galactose, xylose; Sucrose, cycloamylose, cyclodextrin, maltose, trehalose, lactose, sucralose; Sorbitol, maltitol, erythritol, isomalt, lactitol, mannitol, xylitol, sorbitan, lactitol; Starch, cellulose, curdlan, pullulan, alginic acid, carrageenan, guar gum, chitin, chitosan, locust bean gum, kappa carrageenan, iota carrageenan, isomaltodextrin, gellan gum, tamarind seed gum; Ascorbic acid, kojic acid, quinic acid, chlorogenic acid, gluconic acid; Glucosamine; Inositol; Catechins, quercetin, anthocyanins; Ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, glycerol, trimethylolpropane, trimethylolethane; At least one selected from the group consisting of polyglycerin, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymers, hydroxypropyl (meth)acrylate polymers, and hydroxybutyl (meth)acrylate polymers; The repellent according to claim 1 , wherein the hydroxyl group substitution rate in the modified polyol is 30% or more.

14. The polyol modification product is a polyglycerol having a degree of polymerization of 5 to 15, or a sugar alcohol having a hydroxy group represented by the following formula: -O-C(=O)-Z, or -OC(=O)NH-Z [In the formula, Z is an alkyl group having 20 to 24 carbon atoms. is a compound substituted with a group represented by The repellent according to claim 1 , wherein the hydroxyl group substitution rate in the modified polyol is 50% or more.

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

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

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

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

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

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

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

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