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 at least one dispersant selected from the group consisting of a nonionic dispersant, a cationic dispersant, an amphoteric dispersant, and an inorganic dispersant, wherein the volume abundance ratio of particles having a size of 100 μm or more, as measured by laser diffraction scattering, is 25% or less.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a repellent and a product treated with the repellent.

Background Art

[0002] In recent years, the 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 been underway.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] Patent Document 1 does not describe oil resistance. Further, Patent Document 1 has not examined the influence of the particle size of the particles contained in the repellent on oil resistance.

[0005] An object of the present disclosure is to provide a novel repellent capable of imparting oil resistance to a substrate (for example, fiber, paper).

Means for Solving the Problems

[0006] The present disclosure includes the following aspects: [Item 1] A water-dispersible repellent containing a polyol-modified product and at least one dispersant selected from the group consisting of a nonionic dispersant, a cationic dispersant, an amphoteric dispersant, and an inorganic dispersant, wherein the volume abundance ratio of particles of 100 μm or more measured by the laser diffraction scattering method is 25% or less. [Item 2] The water repellent agent according to item 1, wherein the polyol modified body is a compound obtained by modifying a polyol with a monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a monovalent polysiloxane group. [Item 3] The water repellent agent according to item 1 or 2, wherein the polyol modified body has an alkyl group having 6 to 40 carbon atoms which may have a substituent. [Item 4] The polyol modified body is obtained by substituting one or more hydroxy groups of the polyol with a group represented by the following formula: -Y-Z n [In the formula, Y is a 1 + n-valent group composed of one or more selected from the group consisting of Y 1 and Y 2 , and Y 1 is a group composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR’)-, -S-, -S(=O) 2 -, -NR’-, -C(OR’)R’-, and -C(OR’)(-) 2 , -N(-) 2 (wherein R’ is, independently at each occurrence, a hydrogen atom or an organic group having 1 to 30 carbon atoms). Y 2 is a group composed of one or more selected from the group consisting of an optionally substituted aliphatic hydrocarbon group having 2 to 4 carbon atoms, an optionally substituted hydrocarbon aromatic ring, and an optionally substituted heterocyclic ring. Z is an optionally substituted monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group. n is an integer of 1 or more and 3 or less.] The water repellent agent according to any one of items 1 to 3, which is a compound substituted with a group represented by the formula. [Item 5] Y is -O-Y 11 -, or -O-Y 11 -Y 21 -Y 12 - [wherein each symbol is independently at each occurrence, Y 11 is a direct bond, -C(=O)-, -C(=O)-NR'- or -C(=S)-NR'-; Y 21 is an optionally substituted hydrocarbon group having 1 to 40 carbon atoms; Y 12 is -O-, -O-C(=O)-, -O-C(=O)-O-, -C(=O)-NR'-,-O-C(=O)-NR'-,-NR'-,-NR'-C(=O)-,-NR'-C(=O)-O-,-NR'-C(=O)-NR'-,-C(=O)-,-C(=O)-O-,-C(=O)-NR'-,-SO 2 -, -SO 2 NR'-, -C(OR')R'- or -C(OR')(-) 2 .], The defoaming agent according to item 4, which is as described above. [Item 6] The defoaming agent according to any one of items 1 to 5, wherein the polyol is at least one selected from the group consisting of monosaccharides, oligosaccharides, polysaccharides, sugar alcohols, hydroxy acids, amino acids, vitamins, flavonols, hydroxyhydrocarbons, and hydroxy group-containing compound polymers. [Item 7] The polyol is glucose, fructose, galactose, xylose; sucrose, cyclodextrin, 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, isomalto-dextrin, gellan gum, tamarind seed gum; ascorbic acid, kojic acid, quinic acid, chlorogenic acid, gluconic acid; glucosamine; inositol; Catechin, quercetin, anthocyanin; Glycerin, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, trimethylolpropane, trimethylolethane; The water repellent agent according to any one of items 1 to 6, which is at least one selected from the group consisting of polyglycerin, polyvinyl alcohol, hydroxyethyl (meth) acrylate polymer, hydroxypropyl (meth) acrylate polymer, and hydroxybutyl (meth) acrylate polymer. [Item 8] The water repellent agent according to any one of items 1 to 7, wherein the bio-based degree of the polyol modified product is 20% or more. [Item 9] The water repellent agent according to any one of items 1 to 8, wherein the hexadecane contact angle of the polyol modified product is 30° or more. [Item 10] The water repellent agent according to any one of items 1 to 9, wherein the dispersant contains a dispersant other than a fatty acid ester having an HLB value of 7 or more. [Item 11] The polyol modified product is obtained by substituting the hydroxy group of the polyol with the following formula: -Y-Z n [In the formula, Y is -O-Y 11 -, or -O-Y 11 -Y 21 -Y 12 - [In the formula, each symbol is independently in 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 12is -O-, -O-C(=O)-, -O-C(=O)-O-, -C(=O)-NR’-, -O-C(=O)-NR’-, -NR’-, -NR’-C(=O)-, -NR’-C(=O)-O-, -NR’-C(=O)-NR’-, -C(=O)-, -C(=O)-O-, -C(=O)-NR’-, -SO 2 -, -SO 2 NR’-, -C(OR’)R’-, or -C(OR’)(-) 2 is.] is, Z is a hydrocarbon group having 6 to 40 carbon atoms, n is an integer of 1 or more and 3 or less.] is a compound substituted with a group represented by, the polyol is, glucose, fructose, galactose, xylose; sucrose, cyclodextrin, 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, isomalto dextrin, gellan gum, tamarind seed gum; ascorbic acid, kojic acid, quinic acid, chlorogenic acid, gluconic acid; glucosamine; inositol; catechin, quercetin, anthocyanin; glycerin, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, trimethylolpropane, trimethylolethane; At least one selected from the group consisting of polyglycerin, polyvinyl alcohol, hydroxyethyl (meth) acrylate polymer, hydroxypropyl (meth) acrylate polymer, and hydroxybutyl (meth) acrylate polymer, The water-repellent agent according to any one of items 1 to 10, wherein the hydroxy group substitution rate in the polyol-modified product is 30% or more. [Item 12] The polyol-modified product is polyglycerin having a polymerization degree of 5 or more and 15 or less, or a hydroxy group of a sugar alcohol is represented by the following formula: -O-C(=O)-Z, or -O-C(=O)NH-Z [In the formula, Z is an alkyl group having 14 or more and 24 or less carbon atoms.] It is a compound substituted with a group represented by The water-repellent agent according to any one of items 1 to 11, wherein the hydroxy group substitution rate in the polyol-modified product is 50% or more. [Item 13] The water-repellent agent according to any one of items 1 to 12, which is for fiber products or paper products. [Item 14] A product treated with the water-repellent agent according to any one of items 1 to 13. [Item 15] The product according to item 14, which is a fiber product or a paper product. [Item 16] The product according to item 14 or 15, which is oil-resistant paper or water-resistant paper. [Item 17] The product according to any one of items 14 to 16, which is a food packaging material or a food container. [Item 18] A method for manufacturing a treated product, which includes a step of treating a base material with the water-repellent agent according to any one of items 1 to 13. [Item 19] The manufacturing method according to item 18, wherein the treatment is an internal addition treatment. [Effect of the Invention]

[0007] ​The sizing agent in the present disclosure can impart good liquid repellency (particularly oil resistance) to paper products.

Mode for Carrying Out the Invention

[0008] <Definition of Terms> As used herein, the term "n-valent group" means a group having n bonds, that is, a group forming n bonds. Further, the term "n-valent organic group" means 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 means a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, halogen, etc. at the terminal or molecular chain of the hydrocarbon group.

[0009] As used herein, the term "hydrocarbon group" means a group containing carbon and hydrogen, which is a group obtained by removing a hydrogen atom from a hydrocarbon. Such a hydrocarbon group is not particularly limited, but may be, for example, a C 1-20 hydrocarbon group, such as an aliphatic hydrocarbon group, an aromatic hydrocarbon group, etc. The above "aliphatic hydrocarbon group" may be linear, branched or cyclic, and may be saturated or unsaturated. Further, the hydrocarbon group may contain one or more ring structures. The hydrocarbon group may be substituted with one or more substituents when explicitly described.

[0010] In this specification, whether or not expressions such as "independently at each occurrence", "independently of each other", "independently of each other" or similar expressions are explicitly described, unless there is a description to the contrary, when a term (symbol) that may appear multiple times in a chemical structure is defined, the definition is applied independently for each occurrence.

[0011] The chemical structures described in this specification should be understood not to include chemical structures that are recognized by those skilled in the art as chemically impossible or extremely unstable.

[0012] <Water and oil repellent agent>

[0013] The water and oil repellent agent in the present disclosure imparts water and oil repellency (water repellency, oil repellency, oil resistance, and / or water resistance) to a substrate (for example, 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 water and oil repellent agent in the present disclosure can preferably impart oil resistance (oil repellency) and / or water resistance (water repellency) to the substrate, and can preferably impart both oil resistance and water resistance, for example.

[0014] The water and oil repellent agent in the present disclosure is a water-dispersible water and oil repellent agent containing a polyol-modified product and at least one dispersant selected from the group consisting of a nonionic dispersant, a cationic dispersant, an amphoteric dispersant, and an inorganic dispersant, and may be a water and oil repellent agent in which the volume occupancy ratio of particles of 100 μm or more measured by the laser diffraction scattering method is 25% or less.

[0015] The water and oil repellent agent in the present disclosure may not have any 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 water and oil repellent agent in the present disclosure can impart water and oil repellency to the substrate even without containing these fluorine compounds.

[0016] 〔Volume occupancy ratio of particles〕 In the repellent of the present disclosure, the volume occupancy ratio of particles of 100 μm or more measured by the 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, preferably 15% or less, or 5% or less. From the viewpoint of coating properties, it is preferable that the volume occupancy ratio of particles of 100 μm or more is within the above range. The method for making the volume occupancy ratio of particles of 100 μm or more measured by the laser diffraction scattering method 25% or less is not limited. For example, a pulverizer, a homogenizer, or the like may be used to refine the particles in the raw material and / or the dispersion liquid.

[0017] [Volume median diameter] The volume median diameter measured by the laser diffraction scattering method in the repellent of the present disclosure may be 10 nm or more, 30 nm or more, 50 nm or more, or 100 nm or more, preferably 150 nm or more, or 200 nm or more, and may also 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 by the laser diffraction scattering method.

[0018] [Polyol modifier] The polyol modifier in the present disclosure adheres to the substrate and can impart liquid repellency, for example, oil resistance and water resistance, to the substrate.

[0019] [Properties of polyol modifier, etc.] The HD (n-hexadecane) contact angle of the polyol-modified body 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 also be 100° or less, 90° or less, or 75° or less. By having an HD contact angle of the polyol-modified body equal to or greater than the above lower limit, good liquid repellency (especially oil repellency) can be imparted to the substrate. The HD contact angle refers to the static contact angle of the polyol-modified body with respect to the spin-coated film as shown in the examples, which is obtained by dropping 2 μL of HD onto the spin-coated film and measuring the contact angle 1 second after the droplet adheres.

[0020] The water contact angle of the polyol-modified body may be 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 65° or more, 75° or more, 85° or more, 90° or more, or 100° or more, and may also be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. By having a water contact angle of the polyol-modified body equal to or greater than the above lower limit, good liquid repellency (especially water repellency) can be imparted to the substrate. The water contact angle refers to the static contact angle of the polyol-modified body with respect to the spin-coated film as shown in the examples, which is obtained by dropping 2 μL of water onto the spin-coated film and measuring the contact angle 1 second after the droplet adheres.

[0021] The polyol-modified body is preferably a compound having carbon of biobased origin. The biobased content is measured in accordance with ASTM D6866. The biobased content may be 20% or more, preferably 30% or more, more preferably 50% or more, still more preferably 60% or more, still more preferably 70% or more, most preferably 80% or more or 90% or more, for example 100%. A high biobased content means a small amount of use of fossil resource-based materials typified by petroleum and the like. From this perspective, it can be said that the higher the biobased content of the polyol-modified body, the more preferable.

[0022] The polyol-modified product preferably has a biodegradability of 5% or more. Since it reduces the environmental load, the higher such biodegradability is, the more preferable it is. The biodegradability of the polyol-modified product may be, for example, 10% or more, 20% or more, 30% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, preferably 60% or more, more preferably 70% or more, still more preferably 80% or more, and most preferably 90% or more. Such biodegradability may be the biodegradability at the 180-day point defined in JIS K 6953-1 or ASTM D6400.

[0023] The polyol-modified product in the present disclosure may not have any 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 polyol-modified product does not contain these fluorine-containing groups, it can impart liquid repellency to the substrate.

[0024] The polyol-modified product is a polymer having a degree of polymerization of 1 or more. From the viewpoint of improving liquid repellency, the degree of polymerization of the polyol-modified product may be 2 or more, 3 or more, 5 or more, 6 or more, preferably 7 or more, more preferably 8 or more, still more preferably 9 or more. Also, from the viewpoint of improving the handleability of the liquid repellent, it may be 100 or less, preferably 50 or less, more preferably 30 or less, still 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.

[0025] The degree of polymerization in the present disclosure means the average degree of polymerization. The average degree of polymerization in the present disclosure means the polymerization obtained by measuring under the following conditions. When the polyol-modified product in the present disclosure is a polyglycerol-modified product obtained by modifying polyglycerol, the degree of polymerization of the polyol-modified product means the average degree of polymerization of the above polyglycerol. The average degree of polymerization of polyglycerol is the average degree of polymerization (n) calculated from the hydroxyl value by the end group analysis method. Specifically, the average degree of polymerization and the average molecular weight are calculated from the following formulas (Formula 1) and (Formula 2). (Formula 1) Average molecular weight = 74n + 18 (Formula 2) Hydroxyl value = 56110(n + 2) / Average molecular weight The hydroxyl value in the above (Formula 2) is a numerical value that serves as an index for the magnitude of the number of hydroxyl groups contained in polyglycerol. The hydroxyl value is calculated from the amount of potassium hydroxide required to neutralize acetic acid necessary for acetylating the free hydroxyl groups contained in 1 g of polyglycerol, and is calculated in accordance with "Standard Oil Analysis Test Methods (I) Established by the Japan Oil Chemists' Society, 2003 Edition" compiled by the Japan Oil Chemists' Society. The hydroxyl value of the raw material polyglycerol is actually measured according to the above standard oil analysis test method, and the average degree of polymerization and the average molecular weight of polyglycerol can be calculated from the above relational expressions.

[0026] When the polyol-modified product in the present disclosure is a polyvinyl alcohol-modified product obtained by modifying polyvinyl alcohol, the degree of polymerization of the polyol-modified product means the average degree of polymerization of the above polyvinyl alcohol. The average degree of polymerization of polyvinyl alcohol can be measured in accordance with JIS K 6726 Polyvinyl Alcohol Test Method.

[0027] When the polyol-modified product in the present disclosure 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 above polysaccharide. The analysis of the average degree of polymerization of the polysaccharide can be carried out 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 top of the peaks of the respective analysis results obtained by ordinary analysis methods such as HPLC, GC, and HPAEC as follows. As the column, for example, ULTRON PS-80N (8 × 300 mm) manufactured by Shinwa Chemical Industries Co., Ltd. (solvent: water, flow rate: 0.5 ml / min, temperature: 50°C) or TSK-GEL G30000 PWXL (7.8 × 300 mm) manufactured by TOSOH Corporation (solvent: water, flow rate: 0.5 ml / min, temperature: 50°C) is used, and it can be measured by using a differential refractometer as a detector.

[0028] The polyol-modified product may be low molecular weight (for example, weight average molecular weight less than 1500, less than 1000, 500 or less) and / or high molecular weight. The weight average molecular weight of the polyol-modified product may be 100 or more, 200 or more, 300 or more, 400 or more, 500 or more, 1000 or more, 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more, and may also be 1000000 or less, 750000 or less, 500000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 10000 or less, 9000 or less, 8000 or less, 7000 or less, 6000 or less, 5000 or less, 3000 or less, 2000 or less, 1000 or less, or 500 or less.

[0029] The substitution rate of the hydroxy groups 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 also be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, 15% or less, for example 95% or less. Here, the "substitution rate" means the proportion (mol%) of the hydroxy groups derived from the polyol that are modified, and may mean the proportion (mol%) modified by a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group that may have a substituent.

[0030] The residual rate of the hydroxyl groups 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, or 90% or more, for example 5% or more, and may also be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, 15% or less, or 5% or less, for example 50% or less, 30% or less, or 10% or less. Here, the "residual rate" means the proportion (mol%) of the hydroxy groups derived from the polyol that are not modified.

[0031] The number of modifying groups in the modified polyol may be 2 or more, 5 or more, 7 or more, 8 or more, 9 or more, 10 or more, 12 or more, 15 or more, 30 or more, or 50 or more, and may also be 1000 or less, 750 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less. Here, the modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group that may have a substituent.

[0032] The modified group equivalent weight of the polyol-modified product may be 150 or more, 250 or more, 350 or more, 450 or more, 550 or more, 650 or more, 750 or more, or 1000 or more, and may also be 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, or 400 or less. It is the value obtained by dividing the weight average molecular weight of the polyol-modified product by the number of modified groups. Here, the modified group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have a substituent.

[0033] [Structure of the modified group] In the polyol-modified product, one or more hydroxy groups of the polyol are substituted by a modified group. The modified group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have a substituent. From the viewpoint of improving liquid repellency, the polyol-modified product may have an alkyl group having 6 to 40 carbon atoms which may have a substituent (for example, an unsubstituted alkyl group having 6 to 40 carbon atoms).

[0034] (Monovalent hydrocarbon group which may have a substituent) The hydrocarbon group modified with respect to the polyol of the polyol-modified product may be a monovalent hydrocarbon group which may have a substituent.

[0035] The hydrocarbon group may be a monovalent hydrocarbon group having 1 to 40 carbon atoms. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be branched, cyclic or linear, and more preferably linear.

[0036] The number of carbon atoms of the hydrocarbon group may be 1 or more, 3 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, preferably 6 or more, 10 or more, 12 or more, or 16 or more, and may also be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, 25 or less, or 20 or less.

[0037] The hydrocarbon group may have a substituent, but is preferably unsubstituted. Examples of the substituent include -OR’, -N(R’) 2 , -COOR’, and a halogen atom, etc. (wherein, R’ is independently, in 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 (for example, a hydrocarbon group, particularly an aliphatic hydrocarbon group)). The substituent may or may not have an active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the hydrocarbon group having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0038] (monovalent polysiloxane group) The polysiloxane group modified with respect to the polyol of the polyol-modified product may be a monovalent polysiloxane group. Similar to the (monovalent) hydrocarbon group, the (monovalent) polysiloxane group can impart liquid repellency to the substrate.

[0039] The polysiloxane group has the following formula: -[-Si(R s ) 2 -O-] a - [wherein, R s is independently, in each occurrence, a hydrocarbon group having 1 to 40 carbon atoms or a reactive group, a is an integer of 5 or more and 10000 or less.] It may be represented by

[0040] R s is a hydrocarbon group having 1 to 40 carbon atoms or a reactive group.

[0041] Examples of the hydrocarbon group having 1 to 40 carbon atoms include a hydrocarbon group having 1 to 5 carbon atoms and a hydrocarbon group having 6 to 40 carbon atoms.

[0042] Examples of hydrocarbon groups having 1 to 5 carbon atoms include hydrocarbon groups having 1 to 5 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, pentyl group, etc. (particularly aliphatic hydrocarbon groups, particularly alkyl groups, such as methyl group or ethyl group, particularly methyl group).

[0043] The hydrocarbon group having 6 to 40 carbon atoms may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, preferably an aliphatic hydrocarbon group, particularly preferably a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be cyclic, linear or branched, preferably linear. The number of carbon atoms of the hydrocarbon group may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, preferably 10 or more, more preferably 12 or more, and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, more preferably 25 or less.

[0044] Examples of the reactive group are groups having a functional group (for example, hydroxy group, amino group, mercapto group, epoxy group, carboxyl group, halogen-substituted alkyl group, vinyl group, (meth)acrylic group, (meth)acryloyloxy group, and (meth)acrylamide group, hydrogen atom directly bonded to a silicon atom, etc.). These functional groups may be directly bonded to the silicon atom or may be bonded to an organic group directly bonded to the silicon atom. The organic group may be a hydrocarbon group, for example, an alkylene group or a divalent aromatic group. The hydrocarbon group may have 2 to 12 carbon atoms, and as the alkylene group, those having 2 to 10 carbon atoms are preferred. As the divalent aromatic group, those having 6 to 12 carbon atoms are preferred. The reactive group may be a group selected from the group consisting of a hydroxy group, an epoxy ring, a carboxyl group, a (meth)acrylic group, and an amino group, and may be, for example, at least one selected from the group consisting of an epoxy ring, a hydroxy group, a (meth)acrylic group, and a carboxyl group.

[0045] a may be 3 or more, 5 or more, 10 or more, 30 or more, 50 or more, 100 or more, 500 or more, 1000 or more, 2000 or more, or 3000 or more, preferably 10 or more, and may also be 10000 or less, 7500 or less, 5000 or less, 3000 or less, 1500 or less, 1000 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less, preferably 500 or less.

[0046] In the polysiloxane group, R is a hydrocarbon group having 1 to 5 carbon atoms s The amount of s R may be 20 mol% or more, 40 mol% or more, 60 mol% or more, or 80 mol% or more based on the total amount of R, preferably 50 mol% or more, and may also be 100 mol% or less, 90 mol% or less, 80 mol% or less, or 70 mol% or less. For example, 50 mol% or more of the total amount of R groups may be methyl groups or ethyl groups (especially methyl groups). s

[0047] In the polysiloxane group, R is a hydrocarbon group having 6 to 40 carbon atoms s The amount of s R may be 3 mol% or more, 10 mol% or more, 20 mol% or more, or 30 mol% or more based on the total amount of R, and may also be 100 mol% or less, 90 mol% or less, 80 mol% or less, or 70 mol% or less.

[0048] In the polysiloxane group, R is a reactive group s The amount of s R may be 5 mol% or more, 10 mol% or more, 20 mol% or more, or 30 mol% or more based on the total amount of R, and may also be 50 mol% or less, 40 mol% or less, 30 mol% or less, or 20 mol% or less.

[0049] R s groups may be introduced randomly or in blocks, but are preferably random.

[0050] The terminal structure of the above-mentioned polysiloxane group is not limited, but is -OR s , -Si(R s ​) 3 etc. The R of the terminal structure s may have one or more reactive groups. Examples of the reactive groups are as described above, and for example, it may be at least one selected from the group consisting of an epoxy ring, a hydroxy group, a (meth)acrylic group, and a carboxyl group.

[0051] The polysiloxane group may have a linker, and the polyol and the polysiloxane group may be bonded via a linker. Such a linker is not limited, but may be a hydrocarbon group having 1 to 40 carbon atoms (for example, 1 to 20 carbon atoms) which may be interrupted by an oxygen atom, for example, a (poly)oxyalkylene group having 1 to 40 carbon atoms (for example, 1 to 20 carbon atoms).

[0052] Examples of the polysiloxane group include -[-Si(R s ) 2 -O-] a -Si(R s ) 3 -L s1 -[-Si(R s ) 2 -O-] a -Si(R s ) 3 -L s1 -O-L s1 -[-Si(R s ) 2 -O-] a -R s -L s1 -[-Si(R s ) 2 -O-] a -Si(R s ) 3 -L s1 -O-L s1 -[-Si(R s ) 2 -O-] a -R s -L s1 -[-Si(R s ) 2 -O-]a -Si(R s ) 3、 -L s1 -[-Si(R s ) 2 -O-] a -R s [In the formula, R s is, independently at each occurrence, a hydrocarbon group or a reactive group having 1 to 40 carbon atoms, and the terminal R s has one or more reactive groups, R s in the total of the groups, 50 mol% or more is a methyl group, L s1 is a hydrocarbon group having 1 to 20 carbon atoms, a is 5 or more and 10,000 or less. ], JPEG2025081479000001.jpg30169[In the formula, a represents an integer of 0 to 150, b represents an integer of 1 to 150, (a + b) is 5 to 200, and n represents an integer of 0 to 36. ] etc. may be mentioned.

[0053] (-Y-Z n ) In the polyol-modified product in the present disclosure, one or more hydroxy groups of the polyol are represented by the following formula: -Y-Z n [In the formula, Y is a 1 + n-valent group composed of one or more selected from the group consisting of Y 1 and Y 2 , Y 1 is a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O) 2 -, -NR'-, -C(OR')R'-, and -C(OR')(-) 2 , -N(-) 2 (wherein R' is, independently at each occurrence, a hydrogen atom or an organic group having 1 to 30 carbon atoms (for example, 1 to 20, 1 to 10, or 1 to 4 carbon atoms) (for example, a hydrocarbon group, particularly an aliphatic hydrocarbon group)). It is a group composed of one or more selected from the group consisting of. ), Y 2 is a group composed of one or more selected from the group consisting of a divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a divalent to tetravalent hydrocarbon aromatic ring which may have a substituent, and a divalent to tetravalent heterocyclic ring which may have a substituent, Z is a monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a monovalent polysiloxane group, n is an integer of 1 or more and 3 or less.] is substituted by a group represented by.

[0054] (Y) Y is Y 1 and Y 2 is an (1 + n)-valent group composed of one or more selected from the group consisting of, a direct bond, -O-, -C(=O)-, -C(=NR’)-, S-, -S(=O) 2 -, -NR’-, -C(OR’)R’-, and -C(OR’)(-) 2 , -N(-) 2 (wherein R’ is, in each occurrence, independently a hydrogen atom or an organic group having 1 to 30 carbon atoms (for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms) (for example, a hydrocarbon group, particularly an aliphatic hydrocarbon group).) is a group composed of one or more selected from the group consisting of, Y 2 is a group composed of one or more selected from the group consisting of a divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a divalent to tetravalent hydrocarbon aromatic ring which may have a substituent, and a divalent to tetravalent heterocyclic ring which may have a substituent.

[0055] n is the number of Zs bonded to Y and may be an integer of 1 or more and 3 or less. n may be 1 or more, 2 or more, or 3 or more, and may also be 3 or less, 2 or less, or 1 or less, for example, 2 or less.

[0056] The molecular weight of Y may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more, and may also be 3000 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less.

[0057] ○ Y 1 Y 1 is a non-hydrocarbon linker.

[0058] Y 1 is a direct bond or a group with a valence of two or more. Y 1 The valence of may be 2 to 4, 2 to 3, or 2. Y 1 It is preferably not only a direct bond.

[0059] Y 1 The molecular weight of may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and may also be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0060] Y 1 is a direct bond, -O-, -C(=O)-, -S(=O) 2 -, -NR’-, -C(OR’)R’-, and -C(OR’)(-) 2 (wherein, R’ is, independently at each occurrence, a hydrogen atom or an organic group having 1 to 30 carbon atoms (for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms) (for example, a hydrocarbon group, particularly an aliphatic hydrocarbon group)). It may be composed of one or more selected from the group consisting of. Y 1 Examples of include a direct bond, -O-, -O-C(=O)-, -O-C(=O)-O-, -O-C(=O)-NR’-, -NR’-, -NR’-C(=O)-, -NR’-C(=O)-O-, -NR’-C(=O)-NR’-, -C(=O)-, -C(=O)-O-, -C(=O)-NR’-, -SO 2 -, -SO 2 NR’-, -C(OR’)R’-, -C(OR’)(-) 2 etc. (In the formula, R’ is, independently at 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).) are exemplified.

[0061] ○ Y 2 Y 2 is a linker of a hydrocarbon which may have a substituent, a hydrocarbon aromatic ring which may have a substituent, or a heterocycle which may have a substituent.

[0062] Y 2 may be a hydrocarbon group or a non-hydrocarbon group (including a heteroatom). Y 2 may be aliphatic or aromatic. Y 2 may be linear, branched, or cyclic.

[0063] Y 2 is a group having a valence of two or more. Y 2 The valence of may be, for example, 2 to 4, 2 to 3, or 2.

[0064] Y 2 The number of carbon atoms of may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, and may also be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[0065] Y 2It is composed of one or more selected from the group consisting of a C1-C40 aliphatic hydrocarbon group having 2 to 4 valences which may have a substituent, a hydrocarbon aromatic ring having 2 to 4 valences which may have a substituent, and a heterocyclic ring having 2 to 4 valences which may have a substituent.

[0066] The C1-C40 aliphatic hydrocarbon group having 2 to 4 valences may be a cyclic, branched, or straight-chain hydrocarbon group. The C1-C40 aliphatic hydrocarbon group having 2 to 4 valences may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The number of carbon atoms of the C1-C40 aliphatic hydrocarbon group may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more, and may also be 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less. The valence of the aliphatic hydrocarbon group may be 2 or more, 3 or more, or 4, and may also be 4 or less, 3 or less, or 2.

[0067] The aliphatic hydrocarbon group may have a substituent. Examples of the substituent include -OR’, -N(R’) 2 , -COOR’, and halogen atoms, etc. (wherein, in each occurrence, 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)). The substituent may or may not have an active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the 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 also be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0068] Examples of the 2- to 4-valent hydrocarbon aromatic rings include groups obtained by removing 2 to 4 hydrogens from hydrocarbon aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthacene), pentacene, pyrene, and coronene. The number of ring-constituting atoms of the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valence of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, and may be 4 or less, 3 or less, or 2.

[0069] The hydrocarbon aromatic ring may have a substituent. Examples of the substituent include -R’, -OR’, -N(R’) 2 , -COOR’, and halogen atoms, etc. (wherein, in each occurrence, 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 (for example, a hydrocarbon group, particularly an aliphatic hydrocarbon group)). The substituent may or may not have an active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the hydrocarbon aromatic 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.

[0070] The divalent to tetravalent heterocyclic ring may be an aliphatic group or an aromatic group. Examples of the divalent to tetravalent heterocyclic ring include groups obtained by removing 2 to 4 hydrogens 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 heterocyclic ring is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valence of the heterocyclic ring may be 2 or more, 3 or more, or 4, and may be 4 or less, 3 or less, or 2.

[0071] The heterocyclic ring may have a substituent. Examples of the substituent include -R’, -OR’, -N(R’) 2 , -COOR’, and halogen atoms, etc. (wherein, R’ is independently, in 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 (for example, a hydrocarbon group, particularly an aliphatic hydrocarbon group)). The substituent may or may not have an active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the heterocyclic ring 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 also be 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less.

[0072] Y 2 Examples of -Ali- -Cy- -Ali(-) 2 -Cy(-) 2 (-)2 Ali- (-) 2 Cy- (-) 2 Ali(-) 2 (-) 2 Cy(-) 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 a heterocyclic ring.] etc. can be mentioned.

[0073] Y 2 Specific examples of -(CH 2 ) p -(p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having an unsaturated bond with 1 to 40, 1 to 20, or 1 to 10 carbon atoms, a hydrocarbon group having a branched structure with 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH 2 ) q -Cy-(CH 2 ) r -(q and r are each independently 0 to 20, for example 1 to 10, and Cy is a hydrocarbon aromatic ring or a heterocyclic ring) etc. can be mentioned.

[0074] (Examples of Y) Examples of Y will be described. In the following, R’ is, in each occurrence, independently a hydrogen atom or an organic group (for example, a hydrocarbon group, particularly an aliphatic hydrocarbon group) having 1 to 30 carbon atoms (for example, 1 to 20, 1 to 10, or 1 to 4 carbon atoms).

[0075] Examples of Y include, when Y is divalent, -Y 1 -、-Y 1 -Y 2 -、-Y 1 -Y 2 -Y1 - and -Y 1 -Y 2 -Y 1 -Y 2 - and -Y 2 - and -Y 2 -Y 1 - and -Y 2 -Y 1 -Y 2 - and -Y 2 -Y 1 -Y 2 -Y 1 - etc. can be mentioned.

[0076] As an example of Y, when Y is trivalent, -Y 1 (-) 2 , -Y 1 -Y 2 (-) 2 , -Y 1 -(Y 2 ) 2 , -Y 1 -Y 2 -Y 1 (-) 2 , -Y 1 -Y 2 (-Y 1 ) 2 , -Y 1 -(Y 2 -Y 1 ) 2 , -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 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 ; Examples include the following.

[0077] As an example of Y, when Y is tetravalent, -Y 1 (-) 3 、 -Y 1 -Y 2 (-) 3 、 -Y 1 -(Y 2 -) 3 、 -Y 1 -Y 2 -Y 1 (-) 3 、 -Y 1 -Y 2 (-Y 1 -) 3 、 -Y 1 -(Y 2 -Y 1 -) 3 、 -Y 1 -Y 2 -Y 1 -Y 2(-) 3 、 -Y 1 -Y 2 -Y 1 -(Y 2 -) 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 ; Examples include the following.

[0078] Preferred examples of Y include -Y 1 -、 -Y 1 -Y2 -,-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. can be mentioned.

[0079] (Examples of preferable Y) Preferably, Y is -O-Y 11 - or -O-Y 11 -Y 21 -Y 12 - [Wherein, each symbol is independently at each occurrence, Y 11 is a direct bond, -C(=O)-, -C(=O)-NR'- or -C(=S)-NR'-; Y 21 is an optionally substituted hydrocarbon group having 1 to 40 carbon atoms; Y 12 is -O-, -O-C(=O)-, -O-C(=O)-O-, -C(=O)-NR'-,-O-C(=O)-NR'-,-NR'-,-NR'-C(=O)-,-NR'-C(=O)-O-,-NR'-C(=O)-NR'-,-C(=O)-,-C(=O)-O-,-C(=O)-NR'-,-SO 2 -,-SO 2 NR'-,-C(OR')R'- or -C(OR')(-) 2 .], It may be.

[0080] Y 11 is a non-hydrocarbon linker, a direct bond or a polyvalent group.

[0081] 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 also be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0082] Y 11 may be a direct bond, -C(=O)-, -C(=O)-NR’-, or -C(=S)-NR’-.

[0083] Y 21 is a divalent hydrocarbon linker and may be a hydrocarbon group having 1 to 40 carbon atoms.

[0084] Y 21 The number of carbon atoms of Y may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, and may also be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[0085] Here, the hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or linear hydrocarbon group, and may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The hydrocarbon group may have a substituent. Examples of the substituent include -OR’, -N(R’)2, -COOR’, and a halogen atom, etc. (wherein, R’ is, in each occurrence, 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)). The substituent may or may not have an active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the hydrocarbon group having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0086] Y 21Specific examples thereof include -(CH 2 ) p -(where p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having an unsaturated bond with 1 to 40, 1 to 20, or 1 to 10 carbon atoms, a hydrocarbon group having a branched structure with 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH 2 ) q -Cy-(CH 2 ) r -(where q and r are each independently 0 to 20, for example 1 to 10, and Cy is a hydrocarbon aromatic ring or a heterocyclic ring) and the like.

[0087] Y 12 may be -O-, -O-C(=O)-, -O-C(=O)-O-, -O-C(=O)-NR’-, -NR’-, -NR’-C(=O)-, -NR’-C(=O)-O-, -NR’-C(=O)-NR’-, -C(=O)-, -C(=O)-O-, -C(=O)-NR’-, -SO 2 -, -SO 2 NR’-, -C(OR’)R’-, or -C(OR’)(-) 2 and may be.

[0088] [Z] Z is a monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a monovalent polysiloxane group, and the descriptions in the above (monovalent hydrocarbon group which may have a substituent) and (monovalent polysiloxane group) are incorporated herein. The number of carbon atoms of 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, and 1 is preferred. The substituent is preferably OH (hydroxy group).

[0089] [Other modifying groups] The hydroxy group of the polyol is -Y-Z nIt may be substituted with other modifying groups. Examples of the modifying groups are anionic groups and / or cationic groups.

[0090] Examples of the anionic group include monomers having a carboxyl group, a sulfonic acid group, or a phosphoric acid group.

[0091] Examples of the salt of the anionic group include alkali metal salts, alkaline earth metal salts, or ammonium salts, such as methylammonium salts, ethanolammonium salts, triethanolammonium salts, and the like.

[0092] Examples of the cationic group include amino groups, preferably tertiary amino groups and quaternary amino groups. In the tertiary amino group, the two groups bonded to the nitrogen atom are the same or different and are an aliphatic group having 1 to 5 carbon atoms (especially an alkyl group), an aromatic group having 6 to 20 carbon atoms (aryl group), or an araliphatic group having 7 to 25 carbon atoms (especially an aralkyl group, such as a benzyl group (C 6 H 5 -CH 2 -)). In the quaternary amino group, the three groups bonded to the nitrogen atom are the same or different and are an aliphatic group having 1 to 5 carbon atoms (especially an alkyl group), an aromatic group having 6 to 20 carbon atoms (aryl group), or an araliphatic group having 7 to 25 carbon atoms (especially an aralkyl group, such as a benzyl group (C 6 H 5 -CH 2 -)). In the tertiary amino group and the quaternary amino group, the remaining one group bonded to the nitrogen atom may have a carbon-carbon double bond. The cationic group may be in the form of a salt.

[0093] The cationic group which is a salt is a salt with an acid (organic acid or inorganic acid). Organic acids, such as carboxylic acids having 1 to 20 carbon atoms (especially monocarboxylic acids such as acetic acid, propionic acid, butyric acid, stearic acid, etc.) are preferred.

[0094] [Production method] The polyol modifier may be produced by reacting a modifier having a modifying group (or a precursor structure of the modifying group) with the hydroxy group of the polyol.

[0095] (Polyol) A polyol is a compound having two or more hydroxy groups and is a compound that serves as a raw material for a polyol-modified product. A polyol is a compound having two or more hydroxy groups in the molecule. The polyol may be aliphatic or aromatic, but is preferably aliphatic.

[0096] 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.

[0097] When the polyol is a polymer, it may have a hydroxy group and an ether bond in the repeating structure of the monomer unit.

[0098] The polyol may be low molecular weight (for example, 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 also be 1000000 or less, 750000 or less, 500000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 10000 or less, 5000 or less, 3000 or less, 2000 or less, 1000 or less, or 500 or less.

[0099] The number of hydroxy groups possessed by 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 also be 3000 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less.

[0100] The hydroxy equivalent weight of the polyol may be 20 or more, 40 or more, 60 or more, 80 or more, 100 or more, 120 or more, 150 or more, and may also be 1000 or less, 800 or less, 600 or less, 400 or less, 200 or less, 100 or less, or 75 or less. The hydroxy equivalent weight of the polyol is the value obtained by dividing the weight average molecular weight of the polyol by the number of hydroxyl groups.

[0101] 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 the polyol 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.

[0102] Examples of the monosaccharides include glucose, fructose, galactose, xylose, etc.

[0103] Examples of the oligosaccharides include sucrose, cycloamylose, cyclodextrin, maltose, trehalose, lactose, sucralose, etc.

[0104] Examples of the sugar alcohols (reducing sugars) include sorbitol, maltitol, erythritol, isomalt, lactitol, mannitol, xylitol, sorbitan, lactitol, etc.

[0105] Examples of the polysaccharides include starch, cellulose, curdlan, pullulan, alginic acid, carrageenan, guar gum, chitin, chitosan, locust bean gum, kappa carrageenan, iota carrageenan, isomalto dextrin, gellan gum, tamarind seed gum, etc.

[0106] Examples of the hydroxy acids include ascorbic acid, kojic acid, quinic acid, chlorogenic acid, gluconic acid, etc.

[0107] Examples of amino acids include glucosamine and the like.

[0108] Examples of vitamins include ascorbic acid, inositol and the like.

[0109] Examples of flavonols include catechin, quercetin, anthocyanin and the like.

[0110] Examples of hydroxyhydrocarbons include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, glycerin, trimethylolpropane, trimethylolethane and the like. Hydroxyhydrocarbon is a hydrocarbon having a hydroxy group, which may be aromatic or aliphatic, but is preferably aliphatic. When referring to hydroxyhydrocarbon, it may mean hydroxyhydrocarbons other than compounds contained in other groups such as polysaccharides (other hydroxyhydrocarbons).

[0111] Examples of hydroxy group-containing compound polymers include polyglycerin, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymer, hydroxypropyl (meth)acrylate polymer, hydroxybutyl (meth)acrylate polymer and the like.

[0112] Examples of polyether polyols may be compounds obtained by addition polymerization of alkylene oxides to an initiator. Examples of the initiator include compounds having two or more functional hydroxyl groups. For example, the initiator includes propylene glycol, polypropylene glycol, ethylene glycol, polyethylene glycol, glycerin, polyglycerin, trimethylolpropane, triethanolamine, pentaerythritol, ethylenediamine, aromatic diamine, diethylenetriamine, sorbitol, and sucrose. Examples of the alkylene oxide include ethylene oxide and propylene oxide. The polyether polyol obtained by addition polymerization of the alkylene oxide to the initiator is also referred to as a polyoxyalkylene polyol or an oxyalkylene derivative of a polyol. Representative examples of the polyether polyol include, for example, polyoxypropylene triol obtained by addition polymerization of propylene oxide to glycerin, and polyoxypropylene polyglyceryl ether obtained by addition polymerization of propylene oxide to polyglycerin.

[0113] Examples of polymer polyols are compounds obtained by polymerizing at least a part of the polyether polyol with an ethylenically unsaturated monomer in the polyether polyol. Examples of the ethylenically unsaturated monomer include acrylonitrile and styrene.

[0114] Examples of the polyester polyol may be compounds obtained by dehydrative 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 the compound 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 the compound 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.

[0115] (Modifier) The modifier is a compound having reactivity with the polyol, and is preferably a compound having a monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a monovalent polysiloxane group as described above.

[0116] Examples of the modifier are as follows. Acid halide G(O=)C-Z Acid anhydride O(C(=O)-Z) 2 Carboxylic acid HO(O=)C-Z Isocyanate O=C=N-Z Thiocyanate S=C=N-Z Epoxy (CH 2 OCH)CH 2 O-Z Halide G-Z Amine H 2 N-Z Hydroxy HO-Z [In the formula, Z is as described above, and G is a halogen atom (for example, F, Cl, Br, or I).]

[0117] Z in the structure of the above modifier may be replaced with any group constituting the modifying group. For example, Z may be a monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a group having a monovalent polysiloxane group. For example, Z may be -Y-Z n may be used.

[0118] The polyol modifier may be synthesized by reacting a polyol with a modifier. For example, a modifier which is an acid halide compound, an acid anhydride, or a carboxylic acid is reacted with a hydroxy group of a polyol to form an ester bond, thereby synthesizing a polyol modifier. Further, a modifier which is a halide or an epoxy compound is reacted with a hydroxy group of a polyol to form an ether bond, thereby generating a polyol modifier. Those skilled in the art can appropriately design the reaction conditions between the polyol and the modifier, such as the use of a catalyst (for example, an acid catalyst or a base catalyst) and the use of a condensing agent, according to the target product.

[0119] [Dispersant] The water repellent of the present disclosure preferably contains a dispersant.

[0120] The dispersant is selected from an organic dispersant and an inorganic dispersant. It may be at least one kind. The dispersant may be nonionic, and may be at least one kind selected from a nonionic dispersant, a cationic dispersant, an amphoteric dispersant, and an inorganic dispersant. The water repellent may not contain an anionic dispersant. The dispersant may contain a dispersant other than a fatty acid ester having an HLB value of 7 or more. For example, the dispersant may contain a fatty acid ester-based dispersant having an HLB value of less than 7, or may contain a dispersant other than a fatty acid ester.

[0121] The dispersant may be used individually for the organic dispersant and the inorganic dispersant, or may be a combination of the organic dispersant and the inorganic dispersant.

[0122] 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.

[0123] The dispersant may be non-fluorine.

[0124] [Nonionic dispersant] The dispersant may contain a nonionic dispersant. The nonionic dispersant may be a nonionic surfactant.

[0125] The nonionic dispersant may be of low molecular weight or high molecular weight. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 100000 or less, 10000 or less, 7500 or less, 5000 or less, 25000 or less, 750 or less, or 250 or less.

[0126] Examples of nonionic dispersants include ethers, esters, ester ethers, alkanolamides, polyols, and amine oxides.

[0127] Examples of ethers are compounds having an oxyalkylene group (preferably a polyoxyethylene group).

[0128] Examples of esters are esters of alcohols and fatty acids. Examples of alcohols are alcohols having 1 to 30 valences (especially 2 to 10 valences) and 1 to 50 carbon atoms (especially 10 to 30 carbon atoms) (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

[0129] Examples of ester ethers are compounds obtained by adding an alkylene oxide (especially ethylene oxide) to an ester of an alcohol and a fatty acid. Examples of alcohols are alcohols having 1 to 30 valences (especially 2 to 10 valences) and 1 to 50 carbon atoms (especially 3 to 30 carbon atoms) (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

[0130] Examples of alkanolamides are formed from fatty acids and alkanolamines. The alkanolamide may be a monoalkanolamide or a dialkanolamide. Examples of fatty acids are saturated or unsaturated fatty acids 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, with 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0131] The polyol may be an alcohol having 2 to 5 valences and 10 to 30 carbon atoms. The amine oxide may be an oxide (e.g., having 5 to 50 carbon atoms) of an amine (secondary amine or preferably tertiary amine).

[0132] The nonionic dispersant is preferably a nonionic dispersant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms of 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.

[0133] 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.

[0134] Nonionic dispersants may be alkylene oxide adducts of linear and / or branched aliphatic (saturated and / or unsaturated) groups, polyalkylene glycol esters of linear and / or branched fatty acids (saturated and / or unsaturated), sorbitan esters of linear and / or branched fatty acids (saturated and / or unsaturated), glycerin esters of linear and / or branched fatty acids (saturated and / or unsaturated), polyglycerin esters of linear and / or branched fatty acids (saturated and / or unsaturated), sucrose esters of linear and / or branched fatty acids (saturated and / or unsaturated), polyoxyethylene (POE) / polyoxypropylene (POP) copolymers (random copolymers or block copolymers), alkylene oxide adducts of acetylene glycols, etc. 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. Also, the nonionic dispersant may not contain an aromatic group.

[0135] The nonionic dispersant has the formula: R 1 O-(CH 2 CH 2 O) p -(R 2 O) q -R 3 [In the formula, R 1 is an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or an acyl group, each of R 2 is independently the same or different and is an alkylene group having 3 or more carbon atoms (for example, 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 of 2 or more, q is 0 or a number of 1 or more.] It may be a compound represented by

[0136] R1 is preferably 8 to 20 carbon atoms, particularly preferably 10 to 18 carbon atoms. R 1 Preferred specific examples of R include an octyl group, a nonyl group, a trimethylnonyl group, a lauryl group, a tridecyl group, an oleyl group, and a stearyl group. R 2 Examples of R 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, a styrene chain, etc. Among them, an oxypropylene chain is preferred.

[0137] Specific examples of the nonionic dispersant include condensation products of ethylene oxide with hexylphenol, isooctylphenol, hexadecanol, oleic acid, alkane (C 12 -C 16 ) thiol, sorbitan monofatty acid (C 7 -C 19 ) or alkyl (C 12 -C 18 ) amine, 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.

[0138] The proportion of the polyoxyethylene block can be 5 to 80% by weight, for example, 30 to 75% by weight, particularly 40 to 70% by weight, based on the molecular weight of the nonionic dispersant (copolymer). The average molecular weight of the nonionic dispersant is generally 300 to 5,000, for example, 500 to 3,000. The nonionic dispersant may be a single type or a mixture of two or more types. The nonionic dispersant may be a mixture of a compound with an HLB (hydrophilic-lipophilic balance) of less than 15 (especially 5 or less) and a compound with an HLB of 15 or more. Specifically, it is preferably selected from polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene, polyoxypropylene with an HLB 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, polyoxyethylene sorbitan fatty acid esters with an HLB value of less than 7.

[0139] [Cationic dispersant] The dispersant may contain a cationic dispersant. The cationic dispersant may be a cationic surfactant. The cationic dispersant may be of low molecular weight type (for example, with a molecular weight of 2000 or less, especially 10000 or less) or of high molecular weight type (for example, with a molecular weight of 2000 or more). The cationic dispersant may be a compound without an amide group.

[0140] The cationic dispersant may be of low molecular weight type or high molecular weight type. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 100000 or less, 10000 or less, 7500 or less, 5000 or less, 25000 or less, 750 or less, or 250 or less.

[0141] The cationic dispersant may be an amine salt, a quaternary ammonium salt, or an oxyethylene-added ammonium salt. Specific examples of the cationic dispersant are not particularly limited, but include amine salt type dispersants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, etc., and quaternary ammonium salt type dispersants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, benzethonium chloride, etc.

[0142] 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 are hydrocarbon groups having 1 to 40 carbon atoms, X is an anionic group.] It is a compound represented by R 21 , R 22 , R 23 and -R 24 Specific examples of are alkyl groups (for example, methyl group, butyl group, stearyl group, palmityl group). Specific examples of X are halogen (for example, chlorine), acid (for example, hydrochloric acid, acetic acid). The cationic dispersant is particularly preferably a monoalkyltrimethylammonium salt (alkyl having 4 to 40 carbon atoms).

[0143] 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 more (for example, C 12~C 50 ) linear and / or branched aliphatic (saturated and / or unsaturated) groups R 2 is H or a C1-4 alkyl group, benzyl group, polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (especially 2, particularly 3) to 50) (CH 3 、C 2 H 5 is particularly preferred), X is a halogen atom (for example,), C 1 ~C 4 fatty acid base of p is 1 or 2, q is 2 or 3, and p + q = 4.] It may be an ammonium salt represented by. R 1 The number of carbon atoms of may be 12 to 50, for example, 12 to 30.

[0144] Specific examples of the cationic dispersant include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydropolyoxyethylene)ammonium chloride, benzyldodecyldi(hydropolyoxyethylene)ammonium chloride, N-[2-(diethylamino)ethyl]oleamide hydrochloride.

[0145] [Anionic dispersant] The dispersant may contain an anionic dispersant. The anionic dispersant may be an anionic surfactant. The dispersant may not contain an anionic dispersant.

[0146] The anionic dispersant may be of low molecular weight or high molecular weight. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 100000 or less, 10000 or less, 7500 or less, 5000 or less, 25000 or less, 750 or less, or 250 or less.

[0147] Examples of anionic dispersants include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfonated fatty acid salts, N-acyl amino acid type dispersants, phosphoric acid mono- or diester type dispersants, and sulfosuccinic acid esters.

[0148] [Amphoteric Dispersant] The dispersant may contain an amphoteric dispersant. The amphoteric dispersant may be an amphoteric surfactant.

[0149] The amphoteric dispersant may be of low molecular weight or high molecular weight. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 100,000 or less, 10,000 or less, 7500 or less, 5000 or less, 25,000 or less, 750 or less, or 250 or less.

[0150] Examples of amphoteric dispersants include alanines, imidazolinium betaines, amide betaines, betaine acetates, etc. Specifically, lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylaminoacetate betaine, fatty acid amide propyl dimethylaminoacetate betaine, etc. may be mentioned.

[0151] [Inorganic Dispersant] The dispersant may contain an inorganic dispersant.

[0152] 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 also be 100 μm or less, 50 μm or less, 10 μm or less, 1 μm or less, 500 nm or less, or 300 nm or less. The average primary particle size can be measured, for example, by observation with a microscope (scanning electron microscope or transmission electron microscope). The inorganic dispersant may be hydrophilic particles.

[0153] Examples of the inorganic dispersant 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.

[0154] [Amount of dispersant] The amount of the dispersant may be 0.01 part by weight or more, 0.1 part by weight or more, 1 part by weight or more, 3 part by weight or more, 5 part by weight or more, 10 part by weight or more, 15 part by weight or more, 20 part by weight or more, 50 part by weight or more, 75 part by weight or more, or 100 part by weight or more, and may also be 500 part by weight or less, 300 part by weight or less, 200 part by weight or less, 100 part by weight or less, 30 part by weight or less, 20 part by weight or less, 10 part by weight or less, 5 part by weight or less, 3 part by weight or less, or 1 part by weight or less, based on 100 parts by weight of the polyol-modified product.

[0155] [Liquid medium] The repellent in the present disclosure may contain 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 is water-dispersible and may contain at least water.

[0156] Examples of organic solvents 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 hydroxy group (e.g., alcohols, polyols such as glycol-based solvents, ether forms of polyols (e.g., monoether forms), etc.). These may be used alone or in combination of two or more.

[0157] [Amount of liquid medium] The amount of the liquid medium may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, or 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more with respect to 1 part by weight of the polyol-modified body, and may also 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.

[0158] 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 with respect to 1 part by weight of the polyol-modified body, and may also 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.

[0159] 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, based on 1 part by weight of the polyol-modified product, and may also 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.

[0160] [Silicone] The water repellent in the present disclosure may contain silicone (polyorganosiloxane). By containing silicone, in addition to good water repellency, it can also have good texture and durability.

[0161] As the silicone, known silicones can be used. Examples of silicones include polydimethylsiloxane, modified silicones (amino-modified, epoxy-modified silicone, carboxy-modified silicone, methylhydrogen silicone, etc.). The silicone may be a silicone wax having a waxy property. These may be used alone or in combination of two or more.

[0162] The weight average molecular weight of the silicone may be 1000 or more, 10000 or more, or 50000 or more, and may also be 500000 or less, 2500000 or less, 100000 or less, or 50000 or less.

[0163] [Amount of silicone] The amount of silicone may be 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, based on 100 parts by weight of the polyol-modified product, and may also be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0164] 〔Wax〕 The water repellent in the present disclosure may contain wax. By containing wax, good water repellency can be imparted to the substrate.

[0165] Examples of waxes include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin wax (such as polyethylene wax, polypropylene wax, etc.), oxidized polyolefin wax, silicone wax, animal and plant waxes, and mineral waxes. Paraffin wax is preferred. Specific examples of the compounds constituting the wax are normal alkanes (for example, tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane), normal alkenes (for example, 1-eicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, nonacosene, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane). The carbon number of the compounds constituting the wax is preferably 20 to 60, for example, 25 to 45. The molecular weight of the wax may be 200 to 2000, for example, 250 to 1500, 300 to 1000. These may be used alone or in combination of two or more.

[0166] 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.

[0167] [Amount of wax] The amount of the wax may be 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 also be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, based on 100 parts by weight of the polyol-modified product.

[0168] [Organic acid] The release agent of the present disclosure may contain an organic acid. As the organic acid, known ones can be used. Preferred examples of the organic acid include carboxylic acids, sulfonic acids, sulfinic acids, etc., and carboxylic acids are particularly preferred. Examples of the carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid, etc., and formic acid or acetic acid is particularly preferred. In the present disclosure, one kind of organic acid may be used, or two or more kinds may be used in combination. For example, formic acid and acetic acid may be used in combination.

[0169] [Amount of organic acid] The amount of the organic acid may be 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, based on 100 parts by weight of the polyol-modified product. Also, it 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. The amount of the organic acid may be adjusted so that the pH of the release agent is 3 to 10, for example, 5 to 9, particularly 6 to 8. The release agent may be acidic (pH 7 or less, for example, 6 or less).

[0170] 〔Hardening agent〕 The release agent of the present disclosure may contain a hardening agent (active hydrogen-reactive compound or active hydrogen-containing compound).

[0171] The hardening agent (crosslinking agent) in the release agent can cure the polyol-modified product well. The hardening 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 polyol-modified product. 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.

[0172] The hardener may contain 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 (for example, it may be 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.

[0173] Examples of the aliphatic polyisocyanate include aliphatic diisocyanates such as 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-diisocyanatomethyl caproate, and 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 and other aliphatic triisocyanates. These may be used alone or in combination of two or more.

[0174] Examples of alicyclic polyisocyanates include alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of alicyclic polyisocyanates are 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.

[0175] Examples of araliphatic polyisocyanates include araliphatic diisocyanates and araliphatic triisocyanates. Specific examples of araliphatic polyisocyanates 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.

[0176] Examples of aromatic polyisocyanates include 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, etc. These may be used alone or in combination of two or more.

[0177] Derivatives of polyisocyanates include, for example, various derivatives such as dimers, trimers, biurets, allophanates, carbodiimides, uretdiones, uretoimines, isocyanurates, iminooxadiazinediones, etc. of the above-mentioned polyisocyanate compounds. These may be used alone or in combination of two or more.

[0178] 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 obtained by blocking the isocyanate groups of the polyisocyanate compound with a blocking agent. It is preferable to use the blocked polyisocyanate compound because it is relatively stable in solution and can be used in the same solution as the leveling agent.

[0179] The blocking agent blocks the free isocyanate groups. The blocked polyisocyanate compound can, for example, regenerate the isocyanate groups by heating to 100 °C or higher, for example 130 °C or higher, and can easily react with hydroxyl groups. Examples of the blocking agent are phenolic compounds, lactam compounds, aliphatic alcohol compounds, oxime compounds, etc. The polyisocyanate compounds can be used alone or in combination of two or more.

[0180] The epoxy compound is a compound having an epoxy group. Examples of the epoxy compound are epoxy compounds having a polyoxyalkylene group, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether, etc. The chloromethyl group-containing compound is a compound having a chloromethyl group. Examples of the chloromethyl group-containing compound are chloromethyl polystyrene, etc. The carboxyl group-containing compound is a compound having a carboxyl group. Examples of the carboxyl group-containing compound are (poly)acrylic acid, (poly)methacrylic acid, etc.

[0181] Specific examples of the ketone group-containing compound include (poly)diacetone acrylamide, diacetone alcohol, and the like. Specific examples of the hydrazide compound include hydrazine, carbohydrazide, adipic acid hydrazide, and the like. Specific examples of the melamine compound include melamine resin, methyl etherified melamine resin, and the like.

[0182] [Amount of curing agent] The amount of the curing agent may be 0.1 part by weight or more, 1 part by weight or more, 3 part by weight or more, 5 part by weight or more, 10 part by weight or more, 15 part by weight or more, or 20 part by weight or more, 50 part by weight or more, 75 part by weight or more, or 100 part by weight or more, based on 100 parts by weight of the polyol-modified product, and may also be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0183] [Other components] The sizing agent may contain other components in addition to the above components. Examples of other components include polysaccharides, paper strength enhancers, flocculants, yield improvers, coagulants, binder resins, slip preventers, sizing agents, paper strength enhancers, fillers, antistatic agents, preservatives, ultraviolet absorbers, antibacterial agents, deodorants, fragrances, and the like. These may be used alone or in combination of two or more. In addition to the above components, other components may include other water-repellent and / or oil-repellent agents, dispersants, hand modifiers, softeners, flame retardants, paint fixatives, anti-wrinkle agents, drying rate adjusters, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity adjusters, ultraviolet absorbers, antioxidants, pH adjusters, insect repellents, defoamers, shrinkage preventers, anti-wrinkle agents for washing, shape retainers, drape retainers, ironability improvers, brighteners, whitening agents, fabric softening clay, migration inhibitors such as polyvinylpyrrolidone, polymer dispersants, soil release agents, scum dispersants, fluorescent brighteners such as 4,4-bis(2-sulfostyryl)biphenyl disodium (Tinopal CBS-X manufactured by Ciba Specialty Chemicals), dye fixatives, anti-fading agents such as 1,4-bis(3-aminopropyl)piperazine, stain removers, fiber surface modifiers such as enzymes like cellulase, amylase, protease, lipase, keratinase, anti-foaming agents, silk protein powder, surface modified products thereof or emulsion dispersions (e.g., K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical Co., Ltd.), hydrolyzed silk solution (Jomo), Silkgen G Soluble S (Ichimaru Pharcos)) that can impart silk-like hand and functions such as water absorption and release properties, and anti-pollution agents (e.g., nonionic polymer compounds composed of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units (e.g., FR627 manufactured by Gohsei Chemical Industry Co., Ltd.), SRC-1 manufactured by Clariant Japan, etc.). These may be used alone or in combination of two or more.

[0184] [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, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, chitin nanofiber, cellulose nanofiber, and pullulan. The polysaccharides may be substituted modified polysaccharides (excluding the above-mentioned polyol modified products), and in particular, modified polysaccharides into which a hydroxyl group or a cationic group has been introduced.

[0185] [Paper strength enhancer, flocculant, yield improver or coagulant] Examples of paper strength enhancers, flocculants, yield improvers or coagulants include styrene polymers (styrene / maleic acid polymers, styrene / acrylic acid polymers), urea-formaldehyde polymers, polyethyleneimine, melamine-formaldehyde polymers, polyamideamine-epichlorohydrin polymers, polyacrylamide-based polymers, polyamine-based polymers, polydiallyldimethylammonium chloride, alkylamine-epichlorohydrin condensates, condensates of alkylene dichloride and polyalkylene polyamines, dicyandiamide-formalin condensates, dimethyldiallylammonium chloride polymers, and olefin / maleic anhydride polymers, etc.

[0186] [Sizing agent] Examples of sizing agents include cellulose-reactive sizing agents, such as rosin-based sizing agents like rosin soaps, rosin-based emulsions / dispersions, cellulose-reactive sizing agents, such as emulsions / dispersions of acid anhydrides like alkyl and alkenyl succinic anhydrides (ASA), alkenyl and alkyl ketene dimers (AKD) and multimers, and anionic, cationic and amphoteric polymers of ethylenically unsaturated monomers, such as copolymers of styrene and acrylate.

[0187] [Antistatic agent] Examples of antistatic agents include cationic antistatic agents having cationic functional groups such as quaternary ammonium salts, pyridinium salts, primary, secondary, and tertiary amino groups; anionic antistatic agents having anionic functional groups such as sulfonates, sulfate esters, phosphonates, and phosphate esters; amphoteric antistatic agents such as alkyl betaines and their derivatives, imidazolines and their derivatives, alanine and its derivatives; nonionic antistatic agents such as amino alcohols and their derivatives, glycerin and its derivatives, polyethylene glycol and its derivatives, etc. These may also be ionic conductive polymers obtained by polymerizing or copolymerizing monomers having cationic, anionic, or zwitterionic conductive groups. These may be used alone or in combination of two or more.

[0188] [Preservative] Preservatives can be mainly used to enhance the antiseptic power and bactericidal power and maintain the antiseptic property during long-term storage. Examples of preservatives include isothiazolone-based organic sulfur compounds, benzisothiazolone-based organic sulfur compounds, benzoic acids, 2-bromo-2-nitro-1,3-propanediol, etc.

[0189] [UV Absorbent] UV absorbers are agents that have the effect of protecting against ultraviolet rays and are components that absorb ultraviolet rays and convert them into and emit infrared rays, visible light, etc. Examples of UV absorbers include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole-based compounds, 4-t-butyl-4'-methoxybenzoylmethane, etc.

[0190] [Antibacterial Agent] Antibacterial agents are components that have the effect of suppressing the growth of bacteria on fibers and further suppressing the generation of unpleasant odors derived from decomposition products of microorganisms. Examples of antibacterial agents include cationic bactericides such as quaternary ammonium salts, zinc bis-(2-pyridylthio-1-oxide), polyhexamethylene biguanide hydrochloride, 8-hydroxyquinoline, polylysine, etc.

[0191] [Deodorant] Examples of the deodorant include cluster dextrin, methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamidopropyldimethylamine oxide, aminocarboxylic acid-based metal complexes (zinc complex of trisodium methylglycinediacetate described in International Publication No. 2012 / 090580), and the like.

[0192] [Amount of other components] The amount of each or the total amount of other components may be 0.1 part by weight or more, 1 part by weight or more, 3 part by weight or more, 5 part by weight or more, 10 part by weight or more, 15 part by weight or more, 20 part by weight or more, 50 part by weight or more, 75 part by weight or more, or 100 part by weight or more, and may also be 500 part by weight or less, 300 part by weight or less, 200 part by weight or less, 100 part by weight or less, 50 part by weight or less, 40 part by weight or less, 30 part by weight or less, 20 part by weight or less, 10 part by weight or less, or 5 part by weight or less, based on 100 parts by weight of the polyol-modified product.

[0193] <Method for manufacturing a treated fiber product or paper product> The method for manufacturing a product treated with the water-repellent agent in the present disclosure includes a treatment step of treating a substrate with the above-described water-repellent agent.

[0194] "Treatment" means applying the water-repellent agent to the substrate by dipping, spraying, coating, or the like. By the treatment, the polyol-modified product, which is the active ingredient of the water-repellent agent, adheres to the inside and / or surface of the substrate. Here, the adhesion may be physical adhesion or chemical adhesion. For example, the polyol-modified product may be physically or (reactively) chemically modified with the hydroxyl groups of the substrate (fiber, paper, glass, etc.).

[0195] [Substrate] The substrate to be treated with the water-repellent agent in the present disclosure is not limited, but is preferably a fiber product or a paper product, particularly a paper product.

[0196] The sizing agent in the present disclosure imparts liquid repellency to a base material (e.g., a fiber base material, a paper base material), and can function as at least one selected from the group consisting of a water repellent, an oil repellent, an oil resistant agent, and a water resistant agent. The base material treated with the sizing agent in the present disclosure is, for example, oil-resistant paper or water-resistant paper.

[0197] Examples of the base material of the fiber product include animal and plant natural fibers such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semi-synthetic fibers such as rayon and acetate, inorganic fibers such as glass fiber, carbon fiber, and asbestos fiber, or a mixed fiber thereof. Fiber products include woven fabrics, knitted fabrics and non-woven fabrics, fabrics in the form of clothing (e.g., water-repellent clothing, e.g., raincoats), and carpets, and the fibers, yarns, and intermediate fiber products (e.g., slivers or roving, etc.) in the state before being made into a fabric may be treated.

[0198] Examples of the base material of the paper product include paper made from bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, groundwood pulp, bleached or unbleached high-yield pulp such as mechanical pulp or thermomechanical pulp, waste paper pulp such as newspaper waste paper, magazine waste paper, cardboard waste paper or deinked waste paper, paper containers made of paper, molded bodies made of paper, etc. Specific examples of the paper product include food packaging materials, food containers, gypsum board base paper, coated base paper, medium paper, general liners and cores, neutral pure white roll paper, neutral liners, rust-proof liners and metal laminated paper, kraft paper, neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper, molded paper (molded containers), etc., and preferred examples include food packaging materials and food containers.

[0199] The base materials to be treated with the sizing agent of the present disclosure are not limited to textile products or paper products, and other examples 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, coatings, and plaster, etc.

[0200] When the base material is glass, the manufactured glass product may be an optical member. Some layer (or film), such as a hard coat layer or an antireflection layer, etc., may be formed on the surface (outermost layer) of the glass base material. Either a single-layer antireflection layer or a multilayer antireflection layer may be used for the antireflection layer. Examples of inorganic substances that can be used for the antireflection layer include SiO 2 、SiO、ZrO 2 、TiO 2 、TiO、Ti 2 O 3 、Ti 2 O 5 、Al 2 O 3 、Ta 2 O 5 、CeO 2 、MgO、Y 2 O 3 、SnO 2 、MgF 2 、WO 3 and so on. These inorganic substances may be used alone or in combination of two or more of them (e.g., as a mixture). When forming a multilayer antireflection layer, it is preferable to use SiO 2 and / or SiO for its outermost layer. When the article to be manufactured is an optical glass component for a touch panel, a thin film using a transparent electrode, such as indium tin oxide (ITO) or indium zinc oxide, etc., may be provided on a part of the surface of the base material (glass). Also, depending on its specific specifications, etc., the base material may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), a fogging film layer, a hard coating film layer, a polarizing film, a retardation film, and a liquid crystal display module, etc.

[0201] [Treatment Method] The water-repellent agent of the present disclosure can be applied to a substrate by a conventionally known method as a treating agent (particularly a surface treating agent). As a treating method, the water-repellent agent in the present disclosure can be dispersed and diluted in an organic solvent or water if necessary, and then adhered to the inside and / or surface of the substrate and dried by a known method such as dip coating, spray coating, foam coating, etc. After drying, a product with the solid component in the water-repellent agent adhered thereto is obtained. If necessary, it may be applied together with a suitable crosslinking agent and cured. To the water-repellent agent of the present disclosure, if necessary, further, a water- and / or oil-repellent agent, an anti-slip agent, an antistatic agent, a hand modifier, a softening agent, an antibacterial agent, a flame retardant, a paint fixing agent, an anti-wrinkle agent, a drying rate regulator, a crosslinking agent, a film-forming aid, a compatibilizer, an antifreezing agent, a viscosity regulator, an ultraviolet absorber, an antioxidant, a pH regulator, an insect repellent, an antifoaming agent and other various additives can also be used in combination. Examples of the various additives may be the same as those described as "other components" in the above description. The concentration of the water-repellent agent in the treating agent in contact with the substrate may be appropriately changed depending on the use, but may be 0.01 to 10% by weight, for example, 0.05 to 5% by weight.

[0202] The water-repellent agent can be applied to the substrate by any of the methods known for treating the substrate with a liquid. The substrate may be immersed in the water-repellent agent, or a solution may be adhered or sprayed onto the substrate. The treated substrate is preferably dried and cured by heating in order to exhibit water-repellent properties. 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 fiber product is paper, it may be coated on the paper, or a solution may be adhered or sprayed onto the paper, or it may be treated by mixing with a pulp slurry before papermaking. The treatment may be an external addition treatment or an internal addition treatment. Alternatively, the water-repellent agent may be applied to the fiber product by a cleaning method, for example, applied to the fiber product in a washing application or a dry cleaning method, etc.

[0203] [Treatment of Paper Products] Examples of the paper substrate include paper, paper-made containers, and paper-made molded articles (e.g., pulp moldings). The polyol-modified product of the present disclosure can adhere well to the paper substrate.

[0204] Paper can be manufactured by conventionally known papermaking methods. An internal sizing method in which a sizing agent is added to the pulp slurry before papermaking, or an external sizing method in which a sizing agent is applied to the paper after papermaking can be used.

[0205] The size press of the external sizing method can also be classified as follows according to the coating method. One coating method is a so-called pond-type two-roll size press in which a coating liquid (sizing liquid) is supplied to a nip portion formed by passing paper between two rubber rolls to create a coating liquid reservoir called a pond, and the sizing liquid is applied to both sides of the paper by passing the paper through this coating liquid reservoir. Another coating method is a gate roll type in which the sizing liquid is applied by a surface transfer type, and a rod metering size press. In the pond-type two-roll size press, the sizing liquid easily penetrates into the paper, and in the surface transfer type, the sizing liquid components tend to remain on the surface of the paper. The surface transfer type has a coating layer that tends to remain on the surface of the paper and has more coating layers formed on the surface than the pond-type two-roll size press. In the present disclosure, the performance can be imparted to the paper even when the former pond-type two-roll size press is used. The paper treated in this way can show excellent oil resistance, water resistance, etc. by optionally undergoing a heat treatment that can take a temperature range up to 300°C, for example up to 200°C, particularly in the range of 80°C to 180°C, depending on the properties of the paper, after simple drying at room temperature or high temperature.

[0206] The internal addition treatment method may mean a treatment method of adding a sizing agent to the pulp slurry before papermaking. As the internal addition treatment method, it may include one or more of the steps of adding a sizing agent to the pulp slurry and stirring and mixing, sucking and dehydrating the pulp composition prepared in the step through a reticular body of a predetermined shape to deposit the pulp composition to form an intermediate pulp mold, and molding and drying the intermediate pulp mold with a heated mold to obtain paper, a container made of paper, or a molded body made of paper, but it is not limited thereto. The treated paper may be optionally heat-treated depending on the properties of the paper after simple drying at room temperature or 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 also be 300 °C or lower, 250 °C or lower, or 200 °C or lower, particularly 80 °C to 180 °C. By performing the heat treatment within such a temperature range, excellent oil resistance, water resistance, etc. can be exhibited.

[0207] The present disclosure can be used in gypsum board base paper, coated base paper, medium paper, general liner and core, neutral pure white roll paper, neutral liner, rust-proof liner and metal laminated 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.

[0208] As the pulp raw material, bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, groundwood pulp, mechanical pulp or thermomechanical pulp, etc. Any of bleached or unbleached high-yield pulp, waste paper pulp such as newspaper waste paper, magazine waste paper, cardboard waste paper or deinked waste paper can be used. A mixture of the above pulp raw materials and synthetic fibers such as asbestos, polyamide, polyimide, polyester, polyolefin, polyvinyl alcohol, etc. can also be used.

[0209] The water resistance of the paper can be improved by adding a sizing agent. Examples of the sizing agent include cationic sizing agents, anionic sizing agents, and rosin sizing agents (e.g., acidic rosin sizing agents, neutral rosin sizing agents). The amount of the sizing agent may be 0.01 to 5% by weight based on the pulp.

[0210] If necessary, for the paper, as papermaking chemicals used to a normal extent, additives used in the production of paper such as starch, modified starch, carboxymethyl cellulose, paper strength enhancers such as polyamide polyamine-epichlorohydrin resin, flocculants, fixing agents, yield improvers, dyes, fluorescent dyes, slime control agents, defoaming agents, etc. can be used. It is preferable to use starch and modified starch. If necessary, a sizing agent can be applied to the paper by a size press, a gate roll coater, a blade coater, a calender, etc. using starch, polyvinyl alcohol, dyes, coating colors, anti-slip agents, etc.

[0211] In external addition, the amount of the polyol-modified body contained in the coating layer is 0.01 to 2.0 g / m 2 and particularly preferably 0.1 to 1.0 g / m 2 . The coating layer is preferably formed by a sizing agent and starch and / or modified starch. The solid content of the paper sizing agent in the coating layer is preferably 2 g / m 2 or less. In internal addition, it is preferable to mix the sizing agent with the pulp such that the amount of the sizing agent 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, particularly 0.2 to 5.0 parts by weight, based on 100 parts by weight of the pulp forming the paper.

[0212] In external addition, by storing the treatment liquid between rolls and passing the base paper through the treatment liquid between the rolls at an arbitrary roll speed and nip pressure using a so-called pond-type two-roll size press treatment, oil resistance can also be imparted to the paper.

[0213] In the external addition treatment, the paper base material may contain additives such as sizing agents, paper strength enhancers, flocculants, yield agents, or coagulants. The additives may be nonionic, cationic, anionic, or amphoteric. The ionic charge density of the additives is -10000 to 10000 μeq / g, preferably -4000 to 8000 μeq / g, and more preferably -1000 to 7000 μeq / g. Additives (such as sizing agents, paper strength enhancers, flocculants, yield agents, or coagulants) (solid content or active ingredient) can generally be used in an amount of 0.1 to 10% by weight (for example, 0.2 to 5.0% by weight) based on the pulp. In the case of a paper base material containing a cationic additive (for example, a sizing agent, a paper strength enhancer, a flocculant, a yield agent, or a coagulant), the repellent is preferably anionic.

[0214] In the internal addition treatment, it is preferable to form paper from a pulp slurry having a pulp concentration of 0.5 to 5.0% by weight (for example, 2.5 to 4.0% by weight). Additives (such as sizing agents, paper strength enhancers, flocculants, yield agents, or coagulants) and polyol-modified bodies can be added to the pulp slurry. Examples of the additives (such as sizing agents, paper strength enhancers, flocculants, yield agents, or coagulants) include alkyl ketene dimers, alkenyl succinic anhydrides, styrene-based polymers (styrene / maleic acid-based polymers, styrene / acrylic acid-based polymers), urea-formaldehyde polymers, polyethyleneimines, melamine-formaldehyde polymers, polyamideamine-epichlorohydrin polymers, polyacrylamide-based polymers, polyamine-based polymers, polydiallyldimethylammonium chloride, alkylamine·epichlorohydrin condensates, condensates of alkylene dichloride and polyalkylene polyamines, dicyandiamide·formalin condensates, dimethyldiallylammonium chloride polymers, and olefin / maleic anhydride polymers.

[0215] [Pretreatment of Fiber Products] The fiber product may be pretreated before being treated with the repellent of the present disclosure. By performing the pretreatment of the fiber product, excellent fastness can be imparted to the fiber product after being treated with the repellent.

[0216] Examples of the pretreatment of textile products include cationization treatment by reaction with a reactive quaternary ammonium salt, anionic treatment such as sulfonation, carboxylation, phosphorylation, etc., acetylation treatment, benzoylation treatment, carboxymethylation treatment, grafting treatment, tannic acid treatment, polymer coating treatment, etc. after anionic treatment.

[0217] As a method for pretreating textile products, although not limited thereto, the textile products can be pretreated by a conventionally known method. If necessary, the pretreatment liquid can be dispersed and diluted in an organic solvent or water, and adhered to the inside and / or surface of the textile products by a known method such as dip coating, spray coating, foam coating, etc., and then dried. The pH, temperature, etc. of the pretreatment liquid may be adjusted according to the required degree of treatment. As an example of the method for pretreating textile products, the method for pretreating textile products with the above-mentioned treatment agent will be described in detail.

[0218] The pretreatment method of textile products is to introduce -SO 3 M 1 (wherein M 1 represents a monovalent cation), a monovalent group represented by -COOM 2 (wherein M 2 represents a monovalent cation), and -O-P(O)(OX 1 )(OX 2 (wherein X 1 and X 2 each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms), and may include a step of imparting one or more functional groups (hereinafter, also referred to as "specific functional groups") selected from the group consisting of monovalent groups represented by the formula.

[0219] M 1 includes H, K, Na, or an ammonium ion which may have a substituent. M 2 includes H, K, Na, or an ammonium ion which may have a substituent. When X 1 or X 2 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.

[0220] The fiber containing the above specific functional group (hereinafter, may also be referred to as "functional group-containing fiber") can be prepared, for example, by the following method. (i) A compound having the above specific functional group is attached to the fiber material. Note that the attachment of the compound may be in a state where a part of the compound and a part of the fiber are chemically bonded as long as a sufficient amount of the above specific functional group remains. (ii) A fiber in which the above specific functional group is directly introduced into the material constituting the fiber is prepared.

[0221] In the case of (i), for example, a functional group-containing fiber can be obtained by a functional group introduction step of treating the fiber material with a pretreatment liquid containing one or more compounds having the above specific functional group.

[0222] The material of the fiber material is not particularly limited, and examples include natural fibers such as cotton, hemp, silk, and wool, semi-synthetic fibers such as rayon and acetate, synthetic fibers such as polyamide (nylon, etc.), polyester, polyurethane, and polypropylene, and composite fibers, blended fibers, etc. thereof. The form of the fiber material may be any form such as fiber (tow, sliver, etc.), yarn, knitted fabric (including interlaced knitting), woven fabric (including interlacing), and non-woven fabric.

[0223] In the present embodiment, from the viewpoint of improving the water repellency of the obtained fiber product, it is preferable to use a fiber material containing polyamide and polyester as materials, and in particular, nylon such as nylon 6 and nylon 6,6, polyester such as polyethylene terephthalate (PET), polytrimethyl terephthalate, and polylactic acid, and mixed fibers containing these are preferably used.

[0224] The above -SO 3 M 1 As the compound having, a phenolic polymer can be used. Examples of such a phenolic polymer include those containing at least one compound represented by the following general formula.

[0225] JPEG2025081479000002.jpg46169 [wherein, X 2 is -SO 3 M 3 (wherein, M 3 represents a monovalent cation) or a group represented by the following general formula, and n is an integer of 20 to 3000.)

[0226] JPEG2025081479000003.jpg26165 [wherein, M 4 represents a monovalent cation.)

[0227] As the above M 3 , examples include H, K, Na, or an ammonium ion which may have a substituent.

[0228] As the above M 4 , examples include H, K, Na, or an ammonium ion which may have a substituent.

[0229] 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.

[0230] As the compound having the above -COOM 2 , examples include polycarboxylic acid polymers.

[0231] As the polycarboxylic acid polymer, for example, a polymer synthesized by a conventionally known radical polymerization method using acrylic acid, methacrylic acid, maleic acid, etc. as monomers, or a commercially available product can be used.

[0232] As a method for producing a polycarboxylic acid polymer, for example, a method of adding a radical polymerization initiator to an aqueous solution of the above monomer and / or its salt and heating and reacting at 30 to 150 °C for 2 to 5 hours can be mentioned. 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 monomer and / or its salt. Examples of the radical polymerization initiator include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, redox polymerization initiators such as combinations of persulfates and sodium bisulfite, hydrogen peroxide, water-soluble azo polymerization initiators, and the like. These radical polymerization initiators may be used alone or in combination of two or more. Further, during radical polymerization, a chain transfer agent (for example, octyl thioglycolate) may be added for the purpose of adjusting the degree of polymerization.

[0233] In radical polymerization, a comonomer copolymerizable with the above monomer can be used. Examples of the comonomer copolymerizable include vinyl monomers such as ethylene, vinyl chloride, and vinyl acetate, acrylamide, acrylates, and methacrylates. Acrylates and methacrylates preferably have 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 comonomers copolymerizable may be used alone or in combination of two or more.

[0234] The carboxyl group in the polycarboxylic acid polymer may be free or neutralized by an alkali metal, an amine compound, or the like. Examples of the alkali metal include sodium, potassium, and lithium, and examples of the amine compound include ammonia, monoethanolamine, diethanolamine, and triethanolamine.

[0235] From the viewpoint of obtaining a fiber product with good water repellency, the weight average molecular weight of the polycarboxylic acid polymer is preferably from 1,000 to 20,000, more preferably from 3,000 to 15,000.

[0236] As the polycarboxylic acid polymer, commercially available products such as "Neocrystal 770" (manufactured by Nikkawa Chemical Co., Ltd., trade name) and "Cellopol PC-300" (manufactured by Sanyo Chemical Industries, Ltd., trade name) can be used.

[0237] Examples of the compound having -O-P(O)(OX 1 )(OX 2 ) include, for example, phosphate ester compounds represented by the following general formula. JPEG2025081479000004.jpg31165[In the formula, X 1 or X 2 has the same meaning as described above, and X 3 represents an alkyl group having 1 to 22 carbon atoms.]

[0238] As the phosphate ester compound, a phosphoric acid monoester, diester, and triester in which the alkyl ester moiety is an alkyl group having 1 to 22 carbon atoms, and a mixture thereof can be used.

[0239] From the viewpoint of obtaining a fiber product with good water repellency, it is preferable to use lauryl phosphate ester and decyl phosphate ester.

[0240] As the phosphate ester compound, commercially available products such as "Phosphanol ML-200" (manufactured by Toho Chemical Industry Co., Ltd., trade name) can be used.

[0241] The pretreatment liquid containing one or more of the above-mentioned compounds having a specific functional group can be, for example, an aqueous solution of the above-mentioned compounds. Further, the pretreatment liquid may contain an acid, an alkali, a surfactant, a chelating agent, etc.

[0242] Examples of the method for treating the fibrous material with the above pretreatment liquid include padding treatment, dipping treatment, spraying treatment, and coating treatment. Examples of the padding treatment include methods using a padding apparatus described on pages 396 to 397 of the Fiber Dyeing and Finishing Dictionary (published in 1963 by Nikkai Kogyo Shimbunsha) and pages 256 to 260 of Color Dyeing Chemistry III (published in 1975 by Jitskyo Publishing Co., Ltd.). Examples of the coating treatment include methods using a coating machine described on pages 473 to 477 of the General Catalog of Dyeing and Finishing Equipment (published in 1981 by Sen'i Sha). Examples of the dipping treatment include methods using a batch dyeing machine described on pages 196 to 247 of the General Catalog of Dyeing and Finishing Equipment (published in 1981 by Sen'i Sha), and a liquid flow dyeing machine, an air flow dyeing machine, a drum dyeing machine, a winch dyeing machine, a washer dyeing machine, a cheese dyeing machine, etc. can be used. Examples of the spraying treatment include an air spray that atomizes the treatment liquid with compressed air and blows it, and a method using an air spray with a hydraulic atomization method. 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. When the pretreatment liquid contains water, it is preferably dried to remove the water after adhering to the fibrous material. The drying method is not particularly limited, and either a dry heat method or a wet heat method may be used. The drying temperature is not particularly limited, but for example, it may be dried 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.

[0243] When the fibrous material is to be dyed, the treatment with the pretreatment liquid may be performed before dyeing or in the same bath as dyeing. However, when performing reduction soaping, since the compound having the above specific functional group adsorbed in the process (for example, a phenolic polymer compound, etc.) may fall off, it is preferably performed after reduction soaping after dyeing.

[0244] The treatment temperature in the dipping treatment can be 60 to 130°C. The treatment time can be 5 to 60 minutes.

[0245] In the functional group introduction step using the pretreatment liquid, it is preferable to perform the treatment in such an amount that the adhesion amount of the compound having the specific functional group becomes 1.0 to 7.0 parts by weight with respect to 100 parts by weight of the fiber material. When it is within this range, both durable water repellency and texture can be achieved at a high level.

[0246] The pretreatment liquid preferably has its pH adjusted to 3 to 5. For pH adjustment, pH adjusters such as acetic acid and malic acid can be used.

[0247] In the pretreatment liquid, a salt can also 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, sodium carbonate, ammonium sulfate, and sodium sulfate.

[0248] 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 excessively treated. Examples of the removal method include the method by water washing. By performing sufficient removal, it is possible to suppress the inhibition of the expression of water repellency in the subsequent water repellent processing, and in addition, the texture of the obtained fiber product becomes good. Further, the obtained functional group-containing fiber is preferably sufficiently dried before being brought into contact with the above-described treatment agent.

[0249] (ii) Examples of the fiber in which the specific functional group is directly introduced into the material constituting the fiber include cationic dyeable polyester (CD-PET).

[0250] From the viewpoint of good water repellency of the obtained fiber product, the zeta potential of the surface of the functional group-containing fiber is preferably -100 to -0.1 mV, and more preferably -50 to -1 mV. The zeta potential of the surface of the fiber can be measured, for example, with a zeta potential / particle size measurement system ELSZ-1000ZS (manufactured by Otsuka Electronics Co., Ltd.).

[0251] Although the embodiments have been described above, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims.

Example

[0252] Hereinafter, the present disclosure will be described in detail with reference to examples, but the present disclosure is not limited to these examples.

[0253] <Test method> The test procedure is as follows.

[0254] [Volume occupancy ratio of particles of 100 μm or more] From the volume-based frequency distribution (volume distribution) obtained by measurement with a laser diffraction / scattering device for the water-dispersed repellent, the occupancy ratio of particles of 100 μm or more was calculated, and this value was taken as the volume occupancy ratio of particles of 100 μm or more.

[0255] [Median diameter D50] It was determined by measurement with a laser diffraction / scattering device for the water-dispersed repellent.

[0256] [HD contact angle] A solution (or dispersion) with a solid content concentration of 1.0% of the polyol-modified product was spin-coated on a silicon wafer at 2500 rpm for 25 seconds to obtain a spin-coated film. By heating this at 140°C for 1 minute, a silicon wafer treated with the polyol-modified product was produced. Chloroform was used as the solvent or dispersion medium. 2 μL of HD (hexadecane) was dropped onto the silicon wafer treated with the polyol-modified product, and the contact angle 1 second after droplet deposition was taken as the HD contact angle of the polyol-modified product.

[0257] [Water contact angle] A solution (or dispersion) with a solid content concentration of 1.0% of the polyol-modified product was spin-coated onto a silicon wafer at 2500 rpm for 25 seconds to obtain a spin-coated film. By heating this at 140 °C for 1 minute, a silicon wafer treated with the polyol-modified product was produced. Chloroform was used as the solvent or dispersion medium. 2 μL of water was dropped onto the silicon wafer treated with the polyol-modified product, and the contact angle 1 second after droplet deposition was taken as the water contact angle of the polyol-modified product.

[0258] [Production of Pulp Mold] An automatic mold molding machine was used to mold the pulp mold. A reticulated body was placed on top of a metal pulp mold forming die with a large number of suction holes provided at the bottom, and a metal tank was placed on top. A mixture of pulp slurry and a water-dispersible release agent was placed in the upper metal tank. From the side opposite to the side where the reticulated body of the pulp mold forming die was placed, the pulp-containing aqueous composition was suctioned and dehydrated through the pulp mold forming die and the reticulated body by a vacuum pump, and the solid content (such as pulp) contained in the pulp-containing aqueous composition was deposited on the reticulated body to obtain a pulp mold intermediate. Next, the obtained pulp mold intermediate was dried under a pressure of 0.05 - 5 MPa from above and below with a metal osmosis forming die heated to 60 - 250 °C. Thereby, a pulp mold product molded into the shape of a container was manufactured.

[0259] [Normal 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 taken out from the pulp mold, and the degree of oil stain on the pulp mold was evaluated. Evaluation values were set as follows according to the degree of penetration. 5: No stain inside 4: Stain inside. No stain on the back side. 3: Stain inside. Slight stain bleeding on the back side. 2: Stain inside. The stain bleeding to the back is less than 50% of the area. 1: Stain inside. The stain bleeding to the back is 50% or more and less than 100% of the area. 0: Stain bleeding throughout the back side.

[0260] [Normal temperature water resistance test] 100 ml of water at 25 °C was poured into the pulp mold. After leaving it at room temperature for 45 minutes, the water was taken out from the pulp mold, and the degree of wetness of the pulp mold was evaluated. Based on the degree of penetration, the evaluation values were set as follows. 5: No wetness on the inside 4: Wetness on the inside. No wetness on the back side. 3: Wetness on the inside. Slight seepage on the back side. 2: Wetness on the inside. Seepage to the back is less than 50% of the area. 1: Wetness on the inside. Seepage to the back is 50% or more and less than 100% of the area. 0: Seepage throughout the back side.

[0261] [Preparation of treated paper] As wood pulp, a pulp slurry with a weight ratio of LBKP (hardwood bleached kraft pulp) and NBKP (softwood bleached kraft pulp) of 60 wt% and 40 wt%, and a drainage degree of the pulp of 400 ml (Canadian Standard Freeness) was prepared. A wet paper strength agent and a sizing agent were added to this pulp slurry, and using a Fourdrinier paper machine, paper with a basis weight of 45 g / m 3 and a paper density of 0.58 g / cm 2 was used as the base paper for external sizing 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 .

[0262] For this base paper, a treatment liquid in which the compound was dissolved in chloroform at a ratio of 14.9 mg / mL was applied with a Baker applicator with a gap set to 0 mil, and the operation of repeating coating and drying was performed three times, and then dried at 140 °C for 1 minute to produce a treated paper.

[0263] [KIT test (oil resistance)] Measured by 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 the treated paper, and after wiping the test oil after 15 seconds, evaluating based on the presence or absence of oil stain on the treated paper. Tests were conducted using the test oils of Kit Nos. 1 to 6, and the maximum kit number with no stain was taken as the evaluation result of oil resistance.

[0264] [Cone Oil Resistance Test (Oil Resistance)] Place cone oil on the surface of the treated paper, and after wiping the test oil after 15 seconds, evaluate based on the presence or absence of oil stain on the treated paper. When there is no stain, it is marked as ○, and when a stain is visible, it is marked as ×.

Example

[0265] As the polyol modifier, 2 g of decaglycerol dodecabenzoate (degree of polymerization 10, hydroxy group substitution rate: 12 / 12 * 100 [100%], bio-based ratio: 100%), 0.2 g of polyethylene oxide alkyl ether (alkyl carbon number 6 - 16, HLB: 7), and 17.8 g of water were mixed to obtain a precursor A of the water-dispersible release agent. After heating the precursor A of the water-dispersible release agent to 80°C, it was allowed to cool while stirring with a magnetic stirrer to obtain a precursor B of the water-dispersible release agent. The precursor B of the water-dispersible release agent was treated twice under the condition of 100 MPa with a high-pressure wet micronization device to obtain a water-dispersible release agent. The volume occupancy ratio of particles of 100 μm or more in the obtained water-dispersible release agent was 0%, and the median diameter D50 was 6.1 μm. The water-dispersible release agent was added to a pulp slurry with a concentration of 0.5 wt% so that the ratio based on the pulp in terms of solid content was 3.5 wt% to prepare a pulp composition. The pulp composition was put into an automatic mold forming machine to produce a pulp mold. When the pulp mold was subjected to a normal temperature oil resistance test and a normal temperature water resistance test, the results were both 4 points. The results are shown in Table 1.

Example

[0266] As the polyol-modified product, 2 g of decaglycerol dodeca behenyl ester (degree of polymerization: 10, hydroxy group substitution rate: 12 / 12 * 100 [100%], bio-based ratio: 100%), 0.2 g of polyethylene oxide trimethyl nonyl ether (HLB: 13), and 17.8 g of water were mixed to obtain precursor A of the water-dispersible release agent. After heating this precursor A of the water-dispersible release agent to 80°C, it was stirred at 7000 rpm for 20 minutes using a homogenizer to obtain a water-dispersible release agent. The volume occupancy ratio of particles of 100 μm or more and the median diameter D50 of the obtained water-dispersible release agent are shown in Table 1. In the same manner as in Example 1, when subjected to the normal temperature oil resistance test and the normal temperature water resistance test, the results were all 4 points. The results are shown in Table 1.

Example

[0267] A water-dispersible release agent was obtained by the same procedure as in Example 2, except that the amount of polyethylene oxide trimethyl nonyl ether was changed from 0.2 g to 0.1 g. The volume occupancy ratio of particles of 100 μm or more and the median diameter D50 of the obtained water-dispersible release agent are shown in Table 1. In the same manner as in Example 1, it was subjected to the normal temperature oil resistance test and the normal temperature water resistance test. The results are shown in Table 1.

Example

[0268] As the polyol-modified product, 2 g of decaglycerol hepta behenyl ester (degree of polymerization: 10, hydroxy group substitution rate: 7 / 12 * 100 [58%], bio-based ratio: 100%), 0.2 g of polyethylene oxide trimethyl nonyl ether (HLB: 13), and 17.8 g of water were mixed to obtain precursor A of the water-dispersible release agent. After heating this precursor A of the water-dispersible release agent to 80°C, it was stirred at 7000 rpm for 20 minutes using a homogenizer to obtain a water-dispersible release agent. The volume occupancy ratio of particles of 100 μm or more and the median diameter D50 of the obtained water-dispersible release agent are shown in Table 1. The water-dispersible release agent was added to a pulp slurry with a concentration of 0.5 wt% so that the ratio based on the pulp in terms of solid content was 5 wt% to prepare a pulp composition. The pulp composition was put into an automatic mold forming machine to produce a pulp mold. When the pulp mold was subjected to a normal temperature oil resistance test and a normal temperature water resistance test, the oil resistance was 4 points and the water resistance was 4 points.

Example

[0269] A water-dispersible water repellent was obtained in the same manner as in Example 4, except that the polyol modifier was changed to decaglycerol decastearate (degree of polymerization 10, hydroxy group substitution rate: 10 / 12 * 100 [83%], bio-based ratio: 100%). The volume occupancy ratio of particles of 100 μm or more and the median diameter D50 of the obtained water-dispersible water repellent are shown in Table 1. A pulp mold was prepared in the same manner as in Example 4 and subjected to a normal temperature oil resistance test and a normal temperature water resistance test. The results are shown in Table 1.

Example

[0270] A water-dispersible water repellent was obtained in the same manner as in Example 4, except that the polyol modifier was changed to hexaglycerol pentastearate (degree of polymerization 6, hydroxy group substitution rate: 5 / 8 * 100 [63%], bio-based ratio: 100%). The volume occupancy ratio of particles of 100 μm or more and the median diameter D50 of the obtained water-dispersible water repellent are shown in Table 1. In the same manner as in Example 4, it was subjected to a normal temperature oil resistance test and a normal temperature water resistance test. The results are shown in Table 1.

Example

[0271] A water-dispersible water repellent was obtained by the same procedure as in Example 4, except that polyethylene oxide trimethylnonyl ether was changed to polyethylene oxide oleyl ether. The volume occupancy ratio of particles of 100 μm or more and the median diameter D50 of the obtained water-dispersible water repellent are shown in Table 1. In the same manner as in Example 4, it was subjected to a normal temperature oil resistance test and a normal temperature water resistance test. The results are shown in Table 1.

Example

[0272] As a polyol-modified product, 2 g of glycerin trioctadecyl carbonate (degree of polymerization 1, hydroxy group substitution rate: 3 / 3 * 100 [100%]), 0.2 g of polyethylene oxide alkyl ether (alkyl carbon number 6 to 16), and 17.8 g of water were mixed to obtain a precursor A of a water-dispersible water-repellent agent. The precursor A of the water-dispersible water-repellent agent was treated 3 times under the condition of 245 MPa using a high-pressure wet micronization device to obtain a water-dispersible water-repellent agent. The volume occupancy ratio of particles of 100 μm or more in the obtained water-dispersible water-repellent agent was 15%, and the median diameter D50 was 34.1 μm. The water-dispersible water-repellent agent was added to a pulp slurry with a concentration of 0.5 wt% so that the ratio with respect to the pulp was 5 wt% in terms of solid content to prepare a pulp composition. The pulp composition was put into an automatic mold forming machine to produce a pulp mold. When the pulp mold was subjected to a normal temperature oil resistance test and a normal temperature water resistance test, the oil resistance was 4 points and the water resistance was 4 points. The results are shown in Table 1.

Example

[0273] A water-dispersible water-repellent agent was obtained in the same procedure as in Example 4, except that 0.16 g of polyethylene oxide trimethylnonyl ether was changed and 0.04 g of polyethylene oxide alkyl ether (carbon number 6 to 16, HLB: 7) was used. The volume occupancy ratio of particles of 100 μm or more and the median diameter D50 of the obtained water-dispersible water-repellent agent are shown in Table 1. Similar to Example 2, it was subjected to a normal temperature oil resistance test and a normal temperature water resistance test. The results are shown in Table 1.

Example

[0274] A water-dispersible water-repellent agent was obtained in the same procedure as in Example 1, except that polyethylene oxide alkyl ether was changed to benzalkonium chloride. The volume occupancy ratio of particles of 100 μm or more and the median diameter D50 of the obtained water-dispersible water-repellent agent are shown in Table 1. Similar to Example 1, it was subjected to a normal temperature oil resistance test and a normal temperature water resistance test. The results are shown in Table 1.

Example

[0275] Using decaglycerol dodecabenhenyl ester (degree of polymerization: 10, hydroxy group substitution rate: 12 / 12 * 100 [100%], bio-based ratio: 100%) as the polyol modifier, a water-dispersible water repellent was obtained in the same procedure as in Example 2 except that polyethylene oxide trimethylnonyl ether was changed to 0.2 g of sodium oleate. The volume occupancy ratio of particles of 100 μm or more in the obtained water-dispersible water repellent was 0%, and the median diameter D50 was 24.1 μm. The water-dispersible water repellent was added to a 0.5 wt% pulp slurry so that the ratio was 6 wt% with respect to the pulp on a solid content basis to prepare a pulp composition. The pulp composition was put into an automatic mold forming machine to produce a pulp mold. When the pulp mold was subjected to a normal temperature oil resistance test and a normal temperature water resistance test, the oil resistance was 3 points and the water resistance was 3 points.

Example

[0276] A stir bar, 1.8 g of sorbitol, 20 mL of DMF, and 18 g of octadecyl isocyanate were added to a reaction vessel, 1 drop of dibutyltin dilaurate was added, and the mixture was stirred at 60 °C for 1 hour. 1 After confirming the disappearance of octadecyl isocyanate by 1H NMR, the product was washed with hexane and acetone to obtain a sorbitol modifier (hydroxy group substitution rate: 6 / 6 * 100 [100%]) in which sorbitol was modified with octadecyl isocyanate as the polyol modifier. Next, 2 g of the sorbitol modifier was pulverized in a mortar and then mixed with 0.2 g of polyethylene oxide alkyl ether (alkyl carbon number 6 - 16, HLB: 7) and 17.8 g of water to obtain a precursor A of the water-dispersible water repellent. The precursor A of the water-dispersible water repellent was treated 5 times under the condition of 200 MPa using a high-pressure wet micronization device to obtain a water-dispersible water repellent. The volume occupancy ratio of particles of 100 μm or more in the obtained water-dispersible water repellent was 11%, and the median diameter D50 was 16.4 μm. When subjected to a normal temperature oil resistance test and a normal temperature water resistance test in the same manner as in Example 4, the oil resistance was 4 points.

Example

[0277] A stir bar, 5.0 g of polyglycerin (average molecular weight 500), 20 mL of pyridine, and 25 g of octadecyl isocyanate were added to a reaction vessel. One drop of dibutyltin dilaurate was added, and the mixture was stirred at 60°C. After washing, a polyglycerin urethane-modified product (hydroxy group substitution rate: 100%) obtained by modifying polyglycerin with octadecyl isocyanate was obtained as a polyol-modified product. Next, 2 g of the polyglycerin urethane-modified product was mixed with 0.2 g of polyethylene oxide alkyl ether (alkyl carbon number 6 - 16, HLB: 7) and 17.8 g of water to obtain a precursor A of a water-dispersible water repellent. The precursor A of the water-dispersible water repellent was treated 10 times under the condition of 250 MPa using a high-pressure wet micronization device to obtain a water-dispersible water repellent. The volume occupancy ratio of particles of 100 μm or more in the obtained water-dispersible water repellent was 9%, and the median diameter D50 was 11.8 μm. The water-dispersible water repellent was added to a 0.5 wt% pulp slurry so that the ratio based on the pulp in terms of solid content was 8 wt% to prepare a pulp composition. The pulp composition was put into an automatic mold forming machine to produce a pulp mold. When the pulp mold was subjected to a normal temperature oil resistance test and a normal temperature water resistance test, the oil resistance was 4 points and the water resistance was 4 points.

Example

[0278] A stir bar, 1.8 g of mannitol, 20 mL of DMF, and 18 g of octadecyl isocyanate were added to a reaction vessel. One drop of dibutyltin dilaurate was added, and the mixture was stirred at 60°C for 1 hour. After washing with hexane and acetone, a mannitol-modified product (hydroxy group substitution rate: 6 / 6 * 100 [100%]) obtained by modifying mannitol with octadecyl isocyanate was obtained as a polyol-modified product. Next, 2 g of the mannitol-modified product was pulverized in a mortar and then mixed with 0.2 g of polyethylene oxide alkyl ether (alkyl having 6 to 16 carbon atoms, HLB: 7) and 17.8 g of water to obtain precursor A of the water-dispersible release agent. Precursor A of the water-dispersible release agent was treated 5 times under the condition of 200 MPa using a high-pressure wet micronization device to obtain the water-dispersible release agent. The volume occupancy ratio of particles of 100 μm or more in the obtained water-dispersible release agent was 14%, and the median diameter D50 was 18.8 μm. The water-dispersible release agent was added to a 0.5 wt% pulp slurry so that the ratio was 8 wt% based on the pulp in terms of solid content, and a pulp composition was prepared. The pulp composition was put into an automatic mold forming machine to produce a pulp mold. When the pulp mold was subjected to a normal temperature oil resistance test and a normal temperature water resistance test, the oil resistance was 4 points and the water resistance was 4 points.

Example

[0279] Into a reaction vessel, a stir bar, 2.0 g of maltitol, 60 mL of DMSO, and 18.0 g of octadecyl isocyanate were added, 1 drop of dibutyltin dilaurate was added, and after stirring at 60 °C for 1 hour, it was washed with hexane and acetone to obtain a maltitol-modified product in which maltitol was modified with octadecyl isocyanate as a polyol-modified product (hydroxy group substitution rate: 9 / 9 * 100 [100%]). Next, 2 g of the maltitol-modified product was pulverized in a mortar and then mixed with 0.2 g of polyethylene oxide alkyl ether (alkyl having 6 to 16 carbon atoms, HLB: 7) and 17.8 g of water to obtain precursor A of the water-dispersible release agent. Precursor A of the water-dispersible release agent was treated 5 times under the condition of 200 MPa using a high-pressure wet micronization device to obtain the water-dispersible release agent. The volume occupancy ratio of particles of 100 μm or more in the obtained water-dispersible release agent was 18%, and the median diameter D50 was 23.3 μm. The water-dispersible release agent was added to a 0.5 wt% pulp slurry so that the ratio was 8 wt% based on the pulp in terms of solid content, and a pulp composition was prepared. The pulp composition was put into an automatic mold forming machine to produce a pulp mold. When the pulp mold was subjected to a normal-temperature oil resistance test and a normal-temperature water resistance test, the oil resistance was 4 points and the water resistance was 4 points.

Example

[0280] As a polyol modifier, 2 g of decaglycerol dodecabenhenyl ester (degree of polymerization 10, hydroxy group substitution rate: 12 / 12 * 100 [100%], bio-based ratio: 100%), 0.2 g of polyethylene oxide trimethylnonyl ether (HLB: 13), and 17.8 g of water were mixed to obtain a precursor A of a water-dispersible release agent. After heating this precursor A of the water-dispersible release agent to 80 °C, it was stirred at 7000 rpm for 20 minutes with a homogenizer to obtain a water-dispersible release agent. As wood pulp, a pulp slurry with a weight ratio of LBKP (hardwood bleached kraft pulp) and NBKP (softwood bleached kraft pulp) of 60 wt% and 40 wt%, and a drainage degree of the pulp of 400 ml (Canadian Standard Freeness) was prepared. A wet strength agent and a sizing agent were added to this pulp slurry, and paper with a basis weight of 45 g / m 3 and a paper density of 0.58 g / cm 2 was used as the base paper for external sizing 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 . For this base paper, a treatment liquid in which a compound was dissolved in chloroform at a ratio of 14.9 mg / mL was applied with a Baker-type applicator with a gap set to 7 mil, and the operation of repeating drying was performed three times, and then dried at 140 °C for 5 minutes to produce a treated paper. The cone oil resistance of the treated paper was '〇', and the KIT score was 4 points.

Example

[0281] A water-dispersible release agent was obtained in the same manner as in Example 2. 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 solution of cationic starch. A water-dispersible release agent was added to a 0.5 wt% pulp slurry at a ratio of 3.5 wt% based on the pulp on a solids basis. Subsequently, an aqueous solution of cationic starch was added such that the cationic starch was at a ratio of 10 wt% based on the pulp on a solids basis, and a pulp composition was prepared. The pulp composition was put into an automatic mold forming machine to produce a pulp mold. When the pulp mold was subjected to a normal temperature oil resistance test, the result was 4 points. Comparative Example 1

[0282] 2 g of decaglycerol dodecabenzenesulfonate (degree of polymerization 10, substitution rate: 12 / 12 * 100 [100%], bio-based ratio: 100%) as a polyol-modified product, 0.2 g of polyethylene oxide alkyl ether (alkyl carbon number 6 - 16, HLB: 7), and 17.8 g of water were mixed to obtain a precursor A of the water-dispersible release agent. After heating this precursor A of the water-dispersible release agent to 80 °C, it was allowed to cool while stirring with a magnetic stirrer to obtain a water-dispersible release agent. The volume occupancy ratio of particles of 100 μm or more in the obtained water-dispersible release agent was 53%, and the median diameter D50 was 57.1 μm. A water-dispersible release agent was added to a 0.5 wt% pulp slurry at a ratio of 3.5 wt% based on the pulp on a solids basis to prepare a pulp composition. The pulp composition was put into an automatic mold forming machine to produce a pulp mold. When the pulp mold was subjected to a normal temperature oil resistance test and a normal temperature water resistance test, the oil resistance was 1 point and the water resistance was 2 points. Comparative Example 2

[0283] 2 g of decaglycerol dodecabenzenesulfonate (degree of polymerization 10, substitution rate: 12 / 12 * 100 [100%], bio-based ratio: 100%) as a polyol-modified product, 0.2 g of polyethylene oxide alkyl ether (alkyl carbon number 6 - 16, HLB: 7), and 17.8 g of water were mixed to obtain a precursor A of the water-dispersible release agent. After heating this precursor A of the water-dispersible release agent to 80 °C, it was stirred at 1000 rpm for 20 minutes with a homogenizer to obtain a water-dispersible release agent. The volume occupancy ratio of particles of 100 μm or more in the obtained water-dispersible release agent was 41%, and the median diameter D50 was 67.8 μm. A water-dispersible release agent was added to a 0.5 wt% pulp slurry at a ratio of 3.5 wt% based on the pulp on a solids basis to prepare a pulp composition. The pulp composition was put into an automatic mold forming machine to produce a pulp mold. When the pulp mold was subjected to a normal temperature oil resistance test and a normal temperature water resistance test, the oil resistance was 1 point and the water resistance was 2 points. Comparative Example 3

[0284] A water-dispersible release agent was obtained in the same procedure as in Comparative Example 1, except that decaglycerol dodecabenzenesulfonate was used as the polyol-modified body instead of decaglycerol decastearate (degree of polymerization 10, substitution rate: 10 / 12 * 100 [83%], bio-based ratio: 100%), and polyethylene oxide alkyl ether (alkyl carbon number 6 to 16) was used as polyethylene oxide trimethylnonyl ether. The volume occupancy ratio of particles of 100 μm or more and the median diameter D50 of the obtained water-dispersible release agent are shown in Table 1. A pulp mold was produced in the same procedure as in Comparative Example 1, except that the ratio of the water-dispersible release agent was changed to 5 wt% based on the pulp on a solids basis, and when it was subjected to a normal temperature oil resistance test and a normal temperature water resistance test, the oil resistance was 2 points and the water resistance was 2 points. Comparative Example 4

[0285] A water-dispersible release agent was obtained in the same procedure as in Comparative Example 1, except that hexaglycerol pentastearate (degree of polymerization 6, substitution rate: 5 / 8 * 100 [63%], bio-based ratio: 100%) was used as the polyol-modified body. The volume occupancy ratio of particles of 100 μm or more and the median diameter D50 of the obtained water-dispersible release agent are shown in Table 1. A pulp mold was produced in the same procedure as in Comparative Example 1, except that the ratio of the water-dispersible release agent was changed to 5 wt% based on the pulp on a solids basis, and when it was subjected to a normal temperature oil resistance test and a normal temperature water resistance test, the oil resistance was 2 points and the water resistance was 2 points.

[0286]

Table 1

Claims

1. A water-dispersible repellent comprising a modified polyol and at least one dispersant selected from the group consisting of a nonionic dispersant, a cationic dispersant, an amphoteric dispersant, and an inorganic dispersant, A repellent having a volumetric ratio of particles having a size of 100 μm or more of 25% or less as measured by a laser diffraction scattering method.

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

3. The repellent according to claim 1 , wherein the modified polyol has an alkyl group having 6 to 40 carbon atoms which may have a substituent.

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

5. 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)--R-、-O-C(=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 4,

6. 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.

7. The polyol is Glucose, fructose, galactose, xylose; Sucrose, cycloamylose, cyclodextrin, maltose, trehalose, lactose, sucralose; Sorbitol, maltitol, erythritol, isomalt, lactitol, mannitol, xylitol, sorbitan, lactitol; Starch, cellulose, curdlan, pullulan, alginic acid, carrageenan, guar gum, chitin, chitosan, locust bean gum, kappa carrageenan, iota carrageenan, isomaltodextrin, gellan gum, tamarind seed gum; Ascorbic acid, kojic acid, quinic acid, chlorogenic acid, gluconic acid; Glucosamine; Inositol; Catechins, quercetin, anthocyanins; Glycerin, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, trimethylolpropane, trimethylolethane; 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.

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

9. The repellent according to claim 1, wherein the polyol-modified product has a hexadecane contact angle of 30° or more.

10. 2. The repellent of claim 1, wherein the dispersant comprises a dispersant other than a fatty acid ester having an HLB value of 7 or greater.

11. 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; Glycerin, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, trimethylolpropane, trimethylolethane; At least one selected from the group consisting of polyglycerin, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymers, hydroxypropyl (meth)acrylate polymers, and hydroxybutyl (meth)acrylate polymers; The repellent according to claim 1 , wherein the hydroxyl group substitution rate in the modified polyol is 30% or more.

12. 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 14 to 24 carbon atoms. is a compound substituted with a group represented by The hydroxyl group substitution rate in the modified polyol is 50% or more. The repellent according to claim 1.

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

14. A product treated with the repellent according to any one of claims 1 to 13.

15. 15. The product of claim 14 which is a textile product or a paper product.

16. 15. The product of claim 14 which is a greaseproof or waterproof paper.

17. 15. The article of claim 14 which is a food packaging or food container.

18. A method for producing a treated product comprising treating a substrate with a repellent agent according to any one of claims 1 to 13.

19. The method according to claim 18, wherein the treatment is an internal addition treatment.

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