Pulp composition

Abstract

To provide a novel pulp composition having oil resistance and / or water resistance.SOLUTION: Provided is a pulp composition containing a liquid repellent compound and a pulp base material, wherein the liquid repellent compound is a compound having a monovalent C6-C40 hydrocarbon group which may have a substituent and is not a fatty acid ester having a glycoside bond. The pulp base material contains bagasse pulp.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to pulp compositions, particularly pulp compositions having oil resistance and / or water resistance.

Background Art

[0002] Patent Document 1 discloses that a composition containing a sugar fatty acid ester and hemicellulose or lignin can be used for modifying the barrier function of cellulose-based materials.

[0003] In the composition described in Patent Document 1, the sugar fatty acid ester is an essential component, and the case of using other components instead of the sugar fatty acid ester has not been studied. Further, it is not disclosed that excellent oil resistance and water resistance are exhibited by the composition.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] An object of the present disclosure is to provide a novel pulp composition having oil resistance and / or water resistance.

Means for Solving the Problems

[0006] The present disclosure includes the following aspects: [Item 1] A pulp composition comprising a liquid-repellent compound and a pulp base material, wherein the liquid-repellent compound is a compound having a monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, and is not a fatty acid ester having a glycoside bond, and the pulp base material contains bagasse pulp, the pulp composition. [Item 2] The liquid-repellent compound is -OC(=O)R, -COOR, -NHCOR, and -CONHR [wherein each R is independently a monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent.] The pulp composition according to claim 1, having at least one group selected from the group consisting of [Claim 3] The pulp composition according to claim 1 or 2, wherein the liquid-repellent compound is a compound obtained by modifying an amine, a polyol, or a polycarboxylic acid with a hydrocarbon group having 6 to 40 carbon atoms which may have a substituent. [Claim 4] The pulp composition according to any one of claims 1 to 3, wherein the amount of the liquid-repellent compound is 0.5% by weight or more and 25% by weight or less based on the pulp base material. [Claim 5] The pulp composition according to any one of claims 1 to 4, wherein the amount of the bagasse pulp in the pulp base material is 20% by weight or more and 100% by weight or less. [Claim 6] The pulp composition according to any one of claims 1 to 5, wherein the pulp composition contains a dispersant. [Claim 7] The pulp composition according to any one of claims 1 to 6, wherein the pulp composition contains a paper additive. [Claim 8] The pulp composition according to any one of claims 1 to 7, wherein the pulp composition contains a sizing agent. [Claim 9] The pulp composition according to any one of claims 1 to 8, wherein the pulp composition contains a sulfate band. [Claim 10] A pulp molded article formed from the pulp composition according to any one of claims 1 to 9. [Claim 11] The pulp molded article according to claim 10, which is for food contact use. [Claim 12] A method for producing a pulp composition, comprising a step of treating a pulp base material with a liquid-repellent agent containing a liquid-repellent compound, The liquid-repellent compound is a compound having a monovalent hydrocarbon group with 6 to 40 carbon atoms which may have a substituent, and is not a fatty acid ester having a glycoside bond. A method for producing a pulp composition, wherein the pulp base material contains bagasse pulp. [Item 13] The liquid-repellent compound is -OC(=O)R, -COOR, -NHCOR, and -CONHR [In the formula, each R is independently a monovalent hydrocarbon group with 6 to 40 carbon atoms which may have a substituent.] The method for producing a pulp composition according to item 12, having at least one group selected from the group consisting of

Advantages of the Invention

[0007] The pulp composition in the present disclosure can be excellent in oil resistance and / or water resistance.

Modes 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 "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, and is a group obtained by removing a hydrogen atom from a hydrocarbon. Such a hydrocarbon group is not particularly limited, but C 1-20Hydrocarbon groups, such as aliphatic hydrocarbon groups, aromatic hydrocarbon groups, etc., can be mentioned. 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.

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

[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] <Pulp composition> The pulp composition in the present disclosure contains a liquid-repellent compound and a pulp base material. The pulp composition in the present disclosure can be excellent in oil resistance and / or water resistance, preferably both.

[0013] The pulp composition in the present disclosure is obtained by adding a liquid-repellent compound to a pulp base material. The pulp composition may be obtained by treating the pulp base material with a liquid repellent containing a liquid-repellent compound, where the addition amount and composition of the liquid repellent may be adjusted so that each component is in a desired amount. Each component that may be contained in the liquid repellent may be added to the pulp composition as a separate additive.

[0014] The pulp composition in the present disclosure may not have any selected from the group consisting of a compound having a fluoroalkyl group with 8 or more carbon atoms, a compound having a perfluoroalkyl group with 8 or more carbon atoms, a compound having a fluoroalkyl group with 4 or more carbon atoms, a compound having a perfluoroalkyl group with 4 or more carbon atoms, a compound having a perfluoroalkyl group, a compound having a fluoroalkyl group, and a compound having a fluorine atom. The pulp composition in the present disclosure can impart liquid repellency to the substrate even without containing these fluorine compounds.

[0015] The pH of the pulp composition may be 3 to 10, for example 5 to 9, particularly 6 to 8, and the amounts of the respective components may be adjusted so as to obtain such a pH.

[0016] [Pulp substrate] The pulp composition contains a pulp substrate. The pulp substrate is composed of pulp, and the pulp may be wood pulp, non-wood pulp, waste paper pulp, etc., and contains at least bagasse pulp.

[0017] [Wood pulp] Examples of wood pulp include softwood kraft pulp obtained from conifers such as Abies and Pinus, and hardwood kraft pulp obtained from Acacia, Eucalyptus, Fagus, Populus, etc. Examples of softwood kraft pulp include unbleached softwood kraft pulp (NUKP), bleached softwood pulp (NBKP), semi-bleached softwood kraft pulp (NSBKP), and sulfite pulp. Examples of hardwood kraft pulp include unbleached hardwood kraft pulp (LUKP), bleached hardwood kraft pulp (LBKP), semi-bleached hardwood kraft pulp (LSBKP), and sulfite pulp. The pulp used may be used alone or in combination. In addition to kraft pulp, there are also mechanical pulps such as stone groundwood pulp (SGP), pressure groundwood pulp (PGW), refiner groundwood pulp (RGP), thermomechanical pulp (TMP), chemigroundwood pulp (CGP), groundwood pulp (GP), and thermomechanical pulp (TMP) in addition to softwood kraft pulp and hardwood kraft pulp. Furthermore, wastepaper pulp includes deinked wastepaper pulp, deinked and bleached wastepaper pulp, or deinked, bleached, and deinked wastepaper pulp produced from tea wastepaper, kraft envelope wastepaper, magazine wastepaper, newspaper wastepaper, flyer wastepaper, office wastepaper, cardboard wastepaper, high-quality wastepaper, Kent wastepaper, imitation wastepaper, deed wastepaper, etc.

[0018] [Non-wood pulp] Examples of non-wood pulp include pulp obtained from bagasse, kenaf, bamboo, linters, cotton, linen, hemp, ramie, straw, esparto, manila hemp, sisal hemp, jute, flax, ganpi, mitsumata, and kozo.

[0019] [Fiber length of pulp] From the perspective of improving oil resistance, the average fiber length of the pulp is preferably 0.1 mm or more, more preferably 0.3 mm or more, still more preferably 0.5 mm or more, and from the perspective of ease of production, it is preferably 5.0 mm or less, more preferably 4.0 mm or less, still more preferably 3.0 mm or less, particularly preferably 2.0 mm or less, and most preferably 1.2 mm or less.

[0020] [Fiber width of pulp] From the viewpoint of improving oil resistance, the average fiber diameter of the pulp is preferably 5 μm or more, more preferably 10 μm or more, still more preferably 15 μm or more, and preferably 5 0 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less.

[0021] [Composition of pulp base material] The amount of bagasse pulp in the pulp base material may be more than 0% by weight, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, preferably 20% by weight or more, and may also be 100% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, or 10% by weight or less, for example, 80% by weight or less.

[0022] The total amount of pulp other than bagasse pulp in the pulp base material may be 0% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, and may also be 99% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, or 10% by weight or less.

[0023] The amount of wood pulp in the pulp base material may be 0% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, and may also be 99% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, or 10% by weight or less.

[0024] [Form of pulp base material] The form of the pulp base material when the liquid-repellent compound is added may be pulp alone, a pulp slurry, a pulp product, etc. Specific examples include bleached or unbleached chemical pulps such as kraft pulp and sulfite pulp, groundwood pulp, mechanical pulp or thermomechanical pulp, etc., bleached or unbleached high-yield pulp, etc.; pulp slurries containing the pulp; pulp products such as paper, paper containers, and pulp molded articles.

[0025] [Amount of pulp base material] The amount of the pulp base material may be 0.1% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 50% by weight or more, 75% by weight or more, or 90% by weight or more in the pulp composition, and may also be 99% by weight or less, 75% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, 4% by weight or less, or 3% by weight or less. Typically, when the pulp composition is prepared by internal addition, the amount of the pulp base material is 30% by weight or less in the pulp composition, and when the pulp composition is prepared by external addition, the amount of the pulp base material may be 75% by weight or more in the pulp composition.

[0026] The amount of the pulp base material may be 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, 90% by weight or more, 95% by weight or more, or 99% by weight or more in the pulp composition excluding the liquid medium, and may also be 99.9% by weight or less, 95% by weight or less, 90% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, or 55% by weight or less.

[0027] [Liquid medium] The pulp composition may contain a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent, and is typically an aqueous medium, particularly water. The liquid medium may also contain a liquid medium derived from a repellent.

[0028] [Amount of liquid medium] The amount of the liquid medium may be 0.1% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 50% by weight or more, 75% by weight or more, 90% by weight or more, or 95% by weight or more in the pulp composition, and may also be 99% by weight or less, 75% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, 4% by weight or less, or 3% by weight or less. Typically, when the pulp composition is prepared by internal addition, the amount of the liquid medium is 50% by weight or more, particularly 90% by weight or more in the pulp composition, and when the pulp composition is prepared by external addition, the amount of the liquid medium is 30% by weight or less, particularly 10% by weight or less in the pulp composition.

[0029] [Liquid-repellent compound] The pulp composition contains a liquid-repellent compound. For details of the types of liquid-repellent compounds, the description of the liquid-repellent compounds in <Sizing agent> is incorporated by reference.

[0030] [Amount of liquid-repellent compound] The amount of the liquid-repellent compound may be 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more based on the pulp substrate, preferably 0.5% by weight or more, and may also be 25% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, for example 15% by weight or less, 5.0% by weight or less, or 3.0% by weight or less.

[0031] The amount of the liquid-repellent compound which is an amine-modified product may be 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more with respect to the pulp base material, preferably 0.5% by weight or more, and may also be 25% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, for example, 15% by weight or less, 5.0% by weight or less, or 3.0% by weight or less.

[0032] The amount of the liquid-repellent compound which is a polyol-modified product may be 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more with respect to the pulp base material, preferably 0.5% by weight or more, and may also be 25% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, for example, 15% by weight or less, 5.0% by weight or less, or 3.0% by weight or less.

[0033] The amount of the liquid-repellent compound which is a polycarboxylic acid-modified product may be 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more with respect to the pulp base material, preferably 0.5% by weight or more, and may also be 25% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, for example, 15% by weight or less, 5.0% by weight or less, or 3.0% by weight or less.

[0034] The liquid-repellent compound may be externally added to the surface of a pulp base material (e.g., pulp products such as paper, paper containers, and pulp molded products), and the amount of the liquid-repellent compound contained in the coating layer formed by the external addition treatment is 0.01 g / m 2 or more, 0.03 g / m 2 or more, 0.05 g / m 2 or more, 0.1 g / m 2 or more, 0.3 g / m 2 or more, 0.5 g / m 2 or more, or 1.0 g / m 2 or more, and may be 5.0 g / m 2 or less, 4.0 g / m 2 or less, 3.0 g / m 2 or less, 2.0 g / m 2 or less, 1.0 g / m 2 or less, 0.5 g / m 2 or less, 0.3 g / m 2 or less, or 0.1 g / m 2 or less.

[0035] 〔Dispersant〕 The pulp composition may contain a dispersant. For details of the type of the dispersant, the description of the dispersant in <Liquid-repellent agent> is incorporated by reference.

[0036] [Amount of dispersant] The amount of the dispersant may be 0.1 wt% or more, 0.3 wt% or more, 0.5 wt% or more, 0.75 wt% or more, 1.0 wt% or more, 2.0 wt% or more, or 3.0 wt% or more based on the pulp base material, and may also be 10 wt% or less, 7.5 wt% or less, 5.0 wt% or less, 4.0 wt% or less, 3.0 wt% or less, 2.0 wt% or less, 1.0 wt% or less, 0.75 wt% or less, or 0.5 wt% or less, preferably 5.0 wt% or less, more preferably 3.0 wt% or less.

[0037] 〔Paper strengthening agent〕 The pulp composition may contain a paper strengthening agent. Examples of the paper strengthening agent include Polyacrylamide-based paper strengthening agents such as cationic polyacrylamide, anionic polyacrylamide, and amphoteric polyacrylamide; Starch, enzyme-modified starch, thermo-chemically modified starch, oxidized starch, esterified starch, etherified starch (e.g., hydroxyethylated starch, etc.), aldehyde-modified starch, cationized starch, starch, xanthan gum, karaya gum, welan gum, guar gum, pectin, tamarind gum, carrageenan, chitosan, gum arabic, locust bean gum, cellulose, alginic acid, agar, dextran, cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, chitin nanofiber, cellulose nanofiber, and pullulan, polysaccharide sizing agents such as these modified polysaccharides (e.g., modified polysaccharides with hydroxyl groups or cationic groups) etc.; Polyamide sizing agents such as polyamide resin, polyamine resin, polyamide-polyamine resin, polyamide-epichlorohydrin resin, polyamide-polyamine-epichlorohydrin resin, polyamide-polyurea-formaldehyde resin, epoxy-modified polyamide resin, etc.; Urea / melamine sizing agents such as urea resin, melamine resin, urea-formaldehyde resin, melamine-formaldehyde resin, etc.; Polyvinyl alcohol sizing agents such as polyvinyl alcohol, fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, cation-modified polyvinyl alcohol, terminal alkyl-modified polyvinyl alcohol, etc.; Examples include styrene-butadiene copolymer, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, polyacrylate ester, fatty acid diamide, polyethyleneimine resin, ketone aldehyde resin, etc. As the sizing agent in the present disclosure, polyacrylamide sizing agent, polysaccharide sizing agent, or polyamide sizing agent is preferred.

[0038] [Amount of sizing agent] The amount of the sizing agent may be 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more with respect to the pulp, and may also be 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, preferably 5.0% by weight or less.

[0039] [Sizing agent] The pulp composition may contain a sizing agent. Examples of the sizing agent include cationic sizing agents, anionic sizing agents, neutral sizing agents, and amphoteric sizing agents, such as rosin sizing agents (e.g., acidic rosin sizing agents, neutral rosin sizing agents), alkyl ketene dimers, alkenyl succinic anhydrides, and the like.

[0040] [Amount of sizing agent] The amount of the sizing agent may be 0.1% by weight or more, 0.2% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more with respect to the pulp, and may also be 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less.

[0041] [Other additives] In addition to the above, the pulp composition may also contain other additives such as fixing agents (such as aluminum sulfate), coagulants / flocculants (such as polyamine resins), yield improvers (such as polyacrylamide resins), organic acids (such as formic acid, acetic acid), dyes, slime control agents, and antifoaming agents, which are paper-making auxiliary chemicals used in the production of pulp products.

[0042] [Amount of other additives] The amount of other additives may each be 0.01% by weight or more, 0.1% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more with respect to the pulp base material, and may also be 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, 3% by weight or less, or 1% by weight or less.

[0043] <Release agent> The release agent in the present disclosure adheres to a base material (particularly a pulp base material) and can impart liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or antifouling properties to the base material, and can also function as a water repellent, oil repellent, water repellent, oil repellent, and / or antifouling agent.

[0044] The release agent of the present disclosure contains a liquid repellent compound as an active ingredient. The liquid repellent compound itself may be used as a release agent, or may be used as a release agent in combination with other components as described below.

[0045] The release agent in the present disclosure does not have to 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 release agent in the present disclosure can impart liquid repellency to the base material even without containing these fluorine compounds.

[0046] The volume occupancy ratio of particles of 100 μm or more measured by the laser diffraction scattering method in the release agent of the present disclosure may be 0.1% or more, 0.3% or more, 0.5% or more, 1% or more, 1.5% or more, 3% or more, 4% or more, 5% or more, or 10% or more, and may also be 50% or less, 30% or less, 20% or less, 15% or less, 10% or less, 5% or less, 3% or less, or 1.5% or less. The method of setting the volume occupancy ratio of particles of 1 μm or more measured by the laser diffraction scattering method within the above range is not limited, but for example, the particles in the raw material and / or the dispersion liquid may be refined using a pulverizer, a homogenizer, or the like.

[0047] The volume median diameter measured by the laser diffraction scattering method in the sizing agent of the present disclosure may be 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.2 μm or more, 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, 0.6 μm or more, 1.0 μm or more, 5.0 μm or more, 10.0 μm or more, 20.0 μm or more, 30.0 μm or more, 40.0 μm or more, 50.0 μm or more, 75.0 μm or more, or 100.0 μm 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, 10 μm or less, 5 μm or less, 3 μm or less, 1 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, 0.3 μm or less, or 0.2 μm or less, preferably 1 μm or less. 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.

[0048] The average particle diameter obtained from the observation image of a scanning electron microscope of particles obtained by removing the liquid medium by natural drying at room temperature from the sizing agent (for example, an oil-resistant agent for pulp), which is a water-dispersible composition of the present disclosure, may be 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.2 μm or more, 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, or 0.6 μm or more, and may also be 10 μm or less, 5 μm or less, 3 μm or less, 1 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, 0.3 μm or less, or 0.2 μm or less, preferably 1 μm or less. To obtain a particle diameter within the above range, 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. Note that room temperature is 20°C to 30°C, particularly 25°C.

[0049] The ionic charge density in the repellent of the present disclosure may be -1000 μeq / g or more, -800 μeq / g or more, -600 μeq / g or more, -500 μeq / g or more, -400 μeq / g or more, -250 μeq / g or more, -100 μeq / g or more, -50 μeq / g or more, -25 μeq / g or more, 0 μeq / g or more, 1 μeq / g or more, 25 μeq / g or more, 50 μeq / g or more, 100 μeq / g or more, 200 μeq / g or more, preferably -600 μeq / g or more, for example -400 μeq / g or more, -200 μeq / g or more, -50 μeq / g or more. Also, it may be 5000 μeq / g or less, 2500 μeq / g or less, 1000 μeq / g or less, 750 μeq / g or less, 500 μeq / g or less, 400 μeq / g or less, 350 μeq / g or less, 300 μeq / g or less, 200 μeq / g or less, 100 μeq / g or less, or 50 μeq / g or less, preferably 1000 μeq / g or less, more preferably 500 μeq / g or less, for example 300 μeq / g or less. Particularly, the ionic charge density in the repellent of the present disclosure is preferably -600 μeq / g or more and 100 μeq / g or less. The ionic charge density in the repellent of the present disclosure can be measured, for example, by the following method.

[0050] Measure the anion demand of a sample solution with a solid content of 0.1 g / L using a particle charge meter (MUTEK PCD-06 manufactured by BTG) with a 1 / 1000 normal potassium polyvinyl sulfonate solution, and calculate the ionic charge density (cation charge density) from the following formula (1). Alternatively, measure the cation demand in the same manner using a diallyldimethylammonium chloride solution instead of potassium polyvinyl sulfonate, and calculate the ionic charge density (anion charge density) from the following formula (1). Ionic charge density (μeq / g) = A / B (1) A: Cation demand or anion demand (μeq / L) B: Sample solution concentration (g / L)

[0051] 〔Liquid-repellent compound〕 The liquid-repellent compounds in the present disclosure can adhere to a substrate (especially a pulp substrate) and impart liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or antifouling properties, to the substrate.

[0052] [Properties, etc.] The properties that the liquid-repellent compound may have are shown below.

[0053] The HD (n-hexadecane) contact angle of the liquid-repellent compound may be 10° or more, 20° or more, 25° or more, 30° or more, 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 60° or more, or 65° or more, preferably 25° or more, more preferably 30° or more, and may also be 100° or less, 90° or less, or 75° or less. By having an HD contact angle of the liquid-repellent compound 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 is the static contact angle of the spin-coated film of the liquid-repellent compound, and is obtained by dropping 2 μL of HD onto the spin-coated film and measuring the contact angle 1 second after droplet landing.

[0054] The water contact angle of the liquid-repellent compound is 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 liquid-repellent compound 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 is the static contact angle of the spin-coated film of the liquid-repellent compound, and is obtained by dropping 2 μL of water onto the spin-coated film and measuring the contact angle 1 second after droplet landing.

[0055] The liquid-repellent compound is preferably a bio-based compound having carbon of bio-based origin. The bio-based content is measured in accordance with ASTM D6866. The bio-based 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 bio-based content means a small amount of use of fossil resource-based materials typified by petroleum and the like. From such a viewpoint, it can be said that the higher the bio-based content of the liquid-repellent compound, the more preferable.

[0056] The biodegradability of the liquid-repellent compound at the 180-day time point preferably has a biodegradability of 5% or more. Since the environmental load is reduced, the higher such biodegradability, the more preferable. The biodegradability of the liquid-repellent compound at the 180-day time point may be, for example, 10% or more, 20% or more, 30% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, preferably 30% or more, more preferably 50% or more, still more preferably 70% or more, and most preferably 80% or more. The biodegradability of the liquid-repellent compound at the 60-day time point preferably has a biodegradability of 5% or more. Since the environmental load is reduced, the higher such biodegradability, the more preferable. The biodegradability of the liquid-repellent compound at the 60-day time point may be, for example, 10% or more, 15% or more, 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, or 45% or more, preferably 10% or more, more preferably 30% or more. Such biodegradability may be the biodegradability defined in JIS K 6953-1 or ASTM D6400.

[0057] The melting point of the liquid-repellent compound may be 30°C or more, 40°C or more, 60°C or more, 80°C or more, 100°C or more, or 120°C or more, preferably 40°C or more, and may also be 250°C or less, 225°C or less, 200°C or less, 150°C or less, 130°C or less, 120°C or less, 110°C or less, 100°C or less, 80°C or less, or 50°C or less.

[0058] [Structure, etc.] The liquid-repellent compound 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 liquid-repellent compound does not contain these fluorine-containing groups, it can impart liquid repellency to the substrate.

[0059] The liquid-repellent compound may be a compound having a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent. From the viewpoint of liquid repellency, the liquid-repellent compound may have a hydrocarbon group having 6 to 40 carbon atoms (for example, an aliphatic hydrocarbon group).

[0060] (A monovalent hydrocarbon group which may have a substituent) The liquid-repellent compound may have a monovalent hydrocarbon group which may have a substituent.

[0061] The hydrocarbon group may be a monovalent hydrocarbon group having 6 to 40 carbon atoms. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and particularly preferably an aliphatic hydrocarbon group. The hydrocarbon group may be branched, cyclic or linear, and more preferably linear.

[0062] 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, 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.

[0063] The hydrocarbon group may have a substituent, but is preferably unsubstituted. Examples of the substituent include -OR’, -N(R’)2, -COOR’, and a halogen atom, etc. (wherein, R’ is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have an active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the hydrocarbon group having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less. For example, the hydrocarbon group may have 1 to 3 (for example, 1) -OR’ (especially -OH) as a substituent (for example, other than at the terminal).

[0064] The liquid-repellent compound in the present disclosure is preferably not a fatty acid ester having a glycosidic bond. A fatty acid ester having a glycosidic bond is typically a compound having a structure in which a fatty acid is added to a hydroxy group of a compound having a structure with a glycosidic bond (typically a saccharide (monosaccharide or polysaccharide)) by an ester bond. Using such a fatty acid ester may reduce the liquid repellency, which is not preferable.

[0065] [Examples of the liquid-repellent compound] Examples of the liquid-repellent compound include compounds having a hydrocarbon group having 6 to 40 carbon atoms. Examples and preferred ranges of the hydrocarbon group are as described above.

[0066] The liquid-repellent compound is -O(C=O)R, -COOR, -NHCOR, and -CONHR [wherein, R is, independently at each occurrence, a monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent.] and may be a compound having at least one group selected from the group consisting of.

[0067] The liquid-repellent compound may contain an ester group, an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfonamide group, a sulfonylurea group, a sulfonylurethane group, or a sulfonimide group (for example, an ester group, an amide group, a urethane group, a urea group, an imide group). For example, the liquid-repellent compound may contain -C(=O)-O-, -O-C(=O)-, -C(=O)-NR'-, -O-C(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO2NR'- (wherein R' is independently, in each occurrence, a hydrogen atom or a hydrocarbon 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)). The liquid-repellent compound may be a compound in which a raw material compound and a modifying group (particularly a monovalent hydrocarbon group which may have the above-described substituents) are bonded via at least one of these groups. The liquid-repellent compound may contain an amide structure. By the liquid-repellent compound containing at least an amide structure, the liquid repellency can be improved. Here, the amide structure may be an amide structure in a broad sense, and may be selected from amide structures in an amide (acid amide) group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfonamide group, a sulfonylurethane group, a sulfonylurea group, a sulfonimide group, etc. The amide structure may be an amide structure selected from the group consisting of -(C=O)N(-)2, -(C=S)N(-)2, and -S(=O)2N(-)2 (note that each group may be in the direction reversed left and right). Here, at least one of the bonds possessed by N of the amide structure may be bonded to a hydrogen atom. The amide structure is preferably -(C=O)N(-)2, and may be an amide structure in a group selected from the group consisting of an amide group, a urethane group, a urea group, and an imide group.

[0068] More specific examples of the liquid-repellent compound include compounds obtained by modifying an amine, a polyol, or a polycarboxylic acid with a hydrocarbon group having 6 or more and 40 or less carbon atoms which may have a substituent. In the present specification, these are also referred to as an amine-modified product, a polyol-modified product, and a polycarboxylic acid-modified product, respectively, and will be described in detail separately.

[0069] [Amount of liquid-repellent compound] The amount of the liquid-repellent compound may be 0.01% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more in the repellent, and may also be 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, or 3% by weight or less. The liquid-repellent compound alone may be used as the repellent.

[0070] [Amine-modified product] As an example of the liquid-repellent compound, the amine-modified product will be described. The amine-modified product is a compound obtained by chemically modifying an amine compound so as to exhibit liquid repellency.

[0071] In terms of its structure, the amine-modified product in the present disclosure is excellent in dispersibility in a liquid medium, and the repellent of the present disclosure can have stable performance. In the case of a repellent using a polymer-type compound as an active ingredient, the molecular weight distribution is wide and it tends to contain a relatively large amount of impurity components. On the other hand, the amine-modified product can be made low molecular weight and the molecular weight distribution can be narrowed (made single), and the performance can be improved.

[0072] [Structure, etc.] The molecular weight of the amine-modified product may be 200 or more, 300 or more, 350 or more, 400 or more, 500 or more, 550 or more, or 750 or more, and may also be 3000 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 900 or less, 800 or less, 750 or less, or 500 or less.

[0073] The amine-modified product in the present disclosure may not have an active hydrogen-containing group. Examples of the active hydrogen group-containing group include an amino group (an amino group not adjacent to a carbonyl group, for example, a primary or secondary amino group), a hydroxy group, and a carboxyl group. In particular, the amine-modified product in the present disclosure may not have a primary or secondary amino group not adjacent to a carbonyl group.

[0074] The amine-modified product in the present disclosure may be a polyamide having a plurality of amide structures. For example, it may be a polyamide in which a plurality of modifying groups (for example, Z N ) are modified via an amide structure with respect to an amine (raw material amine compound, for example, polyamine). Here, the amide may be an amide structure contained in a urethane group, a urea group, an imide, or the like.

[0075] The amine-modified product may be a compound obtained by modifying an amine (raw material amine compound) with a monovalent hydrocarbon group having 6 to 40 carbon atoms that may have a substituent.

[0076] In the amine-modified product, one or more amino groups of the amine are substituted with a modifying group. The modifying group is preferably a monovalent hydrocarbon group that may have a substituent. From the viewpoint of improving liquid repellency, the amine-modified product may have a structure in which an aliphatic hydrocarbon group having 6 to 40 carbon atoms is modified with respect to the amine.

[0077] Regarding the details of the monovalent hydrocarbon group that may have a substituent, the description of (the monovalent hydrocarbon group that may have a substituent) described above is incorporated herein by reference.

[0078] (Amine skeleton) The amine-modified product in the present disclosure has an amine skeleton. The amine skeleton has one or more amino groups having a predetermined number of bonds (valences), which are obtained by removing a predetermined number of atoms or atomic groups (for example, hydrogen) from an amine compound. The amino group in the amine skeleton means a group selected from the group consisting of -NH2, -NH-, and -N(-)2, and also includes an amino group adjacent to a carbonyl group contained in an amide group, a urethane group, a urea group, an imide, or the like. Note that the amine skeleton may be an aliphatic group or an aromatic group having one or more amino groups, and the presence of heteroatoms other than nitrogen is not excluded.

[0079] The molecular weight of the amine skeleton may be 30 or more, 50 or more, 100 or more, 200 or more, 300 or more, 400 or more, or 500 or more, and may also be 2800 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 600 or less, 450 or less, 300 or less, or 250 or less.

[0080] The number of carbon atoms in the amine skeleton may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, and may also be 100 or less, 80 or less, 60 or less, 40 or less, 30 or less, 20 or less, 10 or less, or 5 or less, preferably 50 or less, particularly 30 or less.

[0081] The amine skeleton has one or more amino groups. The amino group is a mono- to trivalent amino group and is one or more groups selected from the group consisting of -NH2, -NH-, and -N(-)2. The number of amino groups in the amine skeleton may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, preferably 2 or more, and may also be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1.

[0082] The amine skeleton has a hydrocarbon group (aliphatic hydrocarbon group or aromatic hydrocarbon group). The hydrocarbon group may be cyclic, branched, or linear. The hydrocarbon group may be saturated or unsaturated (e.g., saturated). Here, the hydrocarbon group may be interrupted by an oxygen atom and / or a sulfur atom, or may consist only of carbon atoms, nitrogen atoms, and hydrogen atoms. The hydrocarbon group may be a hydrocarbon group interrupted by an oxygen atom and / or a sulfur atom (e.g., a chain saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 hydrocarbon aromatic rings), or may be a general hydrocarbon group (e.g., a chain saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 hydrocarbon aromatic rings). When the hydrocarbon group is interrupted by an oxygen atom and / or a sulfur atom, it will have an ether, thioether, polyether, or polythioether structure. The number of hydrocarbon groups possessed by the amine skeleton may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, and may also be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1.

[0083] The amine skeleton may be composed of a 1- to 3-valent amino group and a chain saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group that may be interrupted by an oxygen atom and / or a sulfur atom.

[0084] The molar ratio (C / N ratio) of carbon atoms to nitrogen atoms in the amine skeleton may be 1 or more, 2 or more, 2.5 or more, 3 or more, 3.5 or more, or 4 or more, and may also be 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3.5 or less, 3 or less, 2.5 or less, or 2 or less, preferably 6 or less or 4 or less.

[0085] (-Y N -Z N n ) The amine-modified product in the present disclosure has the following formula: -Y N -Z N n [In the formula, Y N is a direct bond or a (1 + n)-valent group, Z N is a monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, and n is an integer of 1 to 3.] has one or more groups represented by, at least one -Y N -Z N n may be bonded to the nitrogen atom of the amine skeleton.

[0086] The number of -Y N -Z N n in the amine modifier may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, preferably 2 or more, and may also be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1.

[0087] At least one -Y N -Z N n in the amine modifier is bonded to the nitrogen atom of the amine skeleton. All -Y N -Z N n Among the number of, the ratio of -Y N -Z N n bonded to the nitrogen atom of the amine skeleton may be 10% or more, 30% or more, 60% or more, 80% or more, or 100%, and may also be 100% or less, 95% or less, 75% or less, 50% or less, or 25% or less. -Y N -Z N n not bonded to the nitrogen atom of the amine skeleton may be bonded to other groups (e.g., hydrocarbon groups) of the amine skeleton.

[0088] (Y N ) Y N is a direct bond or a (1 + n)-valent group, preferably a (1 + n)-valent group. Y N functions as a linker connecting the amine skeleton and n Z N s.

[0089] n is Y N Z that binds to N and is a number of 1 or more and 3 or less, and may be an integer. 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.

[0090] Y N may be an aliphatic group (unsaturated aliphatic group or saturated aliphatic group) or an aromatic group.

[0091] Y N The molecular weight of may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more, and may also be 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, or 300 or less.

[0092] Y N may have a carbonyl group. Y N may have one or more selected from the group consisting of an amide group, a urea group, a urethane group, and an imide group, or Y N may form one or more selected from the group consisting of an amide group, a urea group, a urethane group, and an imide together with the amino group in the amine skeleton. Examples of such amide groups, urea groups, urethane groups, and imide groups include -O-C(=O)-NR'- -NR'-C(=O)- -NR'-C(=O)-O- -NR'-C(=O)-NR' -C(=O)-NR'- -C(=O)-NR'-C(=O)- [wherein, R' is a hydrogen atom or a hydrocarbon 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).] are exemplified. Y N is preferably bonded to the nitrogen atom in the amine skeleton via a -(C=O)- group.

[0093] Y Nis a 1+n-valent group composed of one or more selected from the group consisting of direct bond, -O-, -C(=O)-, -C(=NR’)-, -S-, -S(=O)2-, -C(=S)-, -NR’-, -C(OR’)R’-, -C(OR’)(-)2, -N(-)2, a 2-4-valent aliphatic hydrocarbon group having 1-20 carbon atoms, a 2-4-valent hydrocarbon aromatic ring, and a 2-4-valent heterocyclic ring [wherein, R’ is a hydrogen atom or a hydrocarbon group having 1-30 carbon atoms (for example, 1-20, 1-10, or 1-4 carbon atoms).] and may be a 1+n-valent group composed of one or more selected from the group consisting of

[0094] Y N is Y N1 and Y N2 and is a 1+n-valent group composed of one or more selected from the group consisting of Y N1 is a group composed of one or more selected from the group consisting of direct bond, -O-, -C(=O)-, -C(=NR’)-, -S-, -S(=O)2-, -C(=S)-, -NR’-, -C(OR’)R’-, -C(OR’)(-)2, and -N(-)2 (wherein, R’ is independently, in each occurrence, a hydrogen atom or a hydrocarbon group having 1-30 carbon atoms (for example, 1-20, 1-10, or 1-4 carbon atoms).) Y N2 is a group composed of one or more selected from the group consisting of a 2-4-valent aliphatic hydrocarbon group having 1-20 carbon atoms, a 2-4-valent hydrocarbon aromatic ring, and a 2-4-valent heterocyclic ring and may be a 1+n-valent group composed of one or more selected from the group consisting of. In the present specification, Y N The group described as is bonded to the amine skeleton on the left side and Z N on the right side.

[0095] 〇 Y N1 Y N1 is a non-hydrocarbon linker.

[0096] Y N1 is a direct bond or a group having a valency of two or more. The valency of Y N1 may be 2-4, 2-3, or 2.N1 is preferably not only a direct bond.

[0097] Y N1 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.

[0098] Y N1 is composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR’)-, -S-, -S(=O)2-, -C(=S)-, -NR’-, -C(OR’)R’-, -C(OR’)(-)2, and -N(-)2 (wherein R’ is, in each occurrence, independently a hydrogen atom or a hydrocarbon 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)). Y N1 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’-, -C(=O)-NR’-C(=O)-, -C(=NR’)-, -S-, -SO2-, -SO2NR’-, -C(OR’)R’-, -C(OR’)(-)2, -N(-)2 etc. [wherein R’ is, in each occurrence, independently a hydrogen atom or a hydrocarbon 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).] are included. Note that Y N1When it is bonded to the nitrogen atom of the amine skeleton, the nitrogen atom is regarded as a part of the amine skeleton (amino group).

[0099] 〇 Y N2 Y N2 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.

[0100] Y N2 may be a hydrocarbon group or a non-hydrocarbon group (including a heteroatom). Y N2 may be aliphatic or aromatic. Y N2 may be linear, branched, or cyclic.

[0101] Y N2 is a group with a valence of two or more. Y N2 The valence of may be, for example, 2 to 4, 2 to 3, or 2.

[0102] Y N2 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.

[0103] Y N2 is composed of one or more selected from the group consisting of a 2- to 4-valent aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a 2- to 4-valent hydrocarbon aromatic ring which may have a substituent, and a 2- to 4-valent heterocycle which may have a substituent.

[0104] The aliphatic hydrocarbon group having a valence of 2 to 4 and having 1 to 40 carbon atoms may be a cyclic, branched, or linear hydrocarbon group. The aliphatic hydrocarbon group having a valence of 2 to 4 and having 1 to 40 carbon atoms may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The number of carbon atoms of the aliphatic hydrocarbon group having 1 to 40 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more, and may 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.

[0105] The aliphatic hydrocarbon group may have a substituent. Examples of the substituent include -OR’, -N(R’)2, -COOR’, and a halogen atom, etc. (wherein, R’ is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have an active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the 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.

[0106] Examples of the hydrocarbon aromatic ring having a valence of 2 to 4 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 also be 4 or less, 3 or less, or 2.

[0107] The hydrocarbon aromatic ring may have substituents. Examples of the substituents include -R’, -OR’, -N(R’)2, -COOR’, and halogen atoms, etc. (wherein, R’ is independently, in each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituents may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the hydrocarbon aromatic ring having substituents, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0108] The 2- to 4-valent heterocyclic ring may be an aliphatic group or an aromatic group. Examples of the 2- to 4-valent 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 also be 4 or less, 3 or less, or 2.

[0109] The heterocycle may have a substituent. Examples of the substituent include -R’, -OR’, -N(R’)2, -COOR’, and a halogen atom, etc. (wherein R’ is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have an active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the heterocycle having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, for example 65 mol% or more, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less.

[0110] Y N2 Examples of -Ali- -Cy- -Ali(-)2 -Cy(-)2 (-)2Ali- (-)2Cy- (-)2Ali(-)2 (-)2Cy(-)2 -Ali-Cy- -Cy-Ali- -Cy-Ali-Cy- -Ali-Cy-Ali- [wherein Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and Cy is a hydrocarbon aromatic ring or a heterocycle.] etc. are included.

[0111] Y N2 Specific examples of -(CH2) 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, -(CH2) q -Cy-(CH2) 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.

[0112] ·Y N Examples of Y N Examples of will be described. In the following, R’ is, in each occurrence, independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20, 1 to 10, or 1 to 4 carbon atoms).

[0113] Y N Examples of Y include, when Y N is divalent, -Y N1 -, -Y N1 -Y N2 -, -Y N1 -Y N2 -Y N1 -, -Y N1 -Y N2 -Y N1 -Y N2 -, -Y N2 -, -Y N2 -Y N1 -, -Y N2 -Y N1 -Y N2 -, -Y N2 -Y N1 -Y N2 -Y N1 -, etc. can be mentioned.

[0114] Y N Examples of Y include, when Y N is trivalent, -Y N1 (-)2, -Y N1 -Y N2 (-)2, -Y N1 -(Y N2 -)2, -Y N1 -Y N2 -Y N1 (-)2, -Y N1 -Y N2 (-Y N1 -)2, -Y N1 -(Y N2 -YN1 -)2, -Y N1 -Y N2 -Y N1 -Y N2 (-)2, -Y N1 -Y N2 -Y N1 -(Y N2 -) 2、 -Y N1 -Y N2 -(Y N1 -Y N2 -) 2、 -Y N1 -(Y N2 -Y N1 -Y N2 -)2; -Y N2 (-)2, -Y N2 -Y N1 (-)2, -Y N2 -(Y N1 (-)2, -Y N2 -Y N1 -Y N2 (-)2, -Y N2 -Y N1 (-Y N2 (-)2, -Y N2 -(Y N1 -Y N2 (-)2, -Y N2 -Y N1 -Y N2 -Y N1 (-)2, -Y N2 -Y N1 -Y N2 -(Y N1 -) 2、 -Y N2 -Y N1 -(Y N2 -Y N1 -) 2、 -Y N2 -(Y N1 -Y N2 -Y N1 Examples include -)2, etc.

[0115] Y N As an example of Y N when it is tetravalent, -Y N1 (-)3, -Y N1 -Y N2 (-)3, -Y N1 -(YN2 -), 3, -Y N1 -Y N2 -Y N1 (-), 3, -Y N1 -Y N2 (-Y N1 -), 3, -Y N1 -(Y N2 -Y N1 -), 3, -Y N1 -Y N2 -Y N1 -Y N2 (-), 3, -Y N1 -Y N2 -Y N1 -(Y N2 -), 3、 -Y N1 -Y N2 -(Y N1 -Y N2 -), 3、 -Y N1 -(Y N2 -Y N1 -Y N2 -), 3; -Y N2 (-), 3, -Y N2 -Y N1 (-), 3, -Y N2 -(Y N1 -), 3, -Y N2 -Y N1 -Y N2 (-), 3, -Y N2 -Y N1 (-Y N2 (-), 3, -Y N2 -(Y N1 -Y N2 (-), 3, -Y N2 -Y N1 -Y N2 -Y N1 (-), 3, -Y N2 -Y N1 -Y N2 -(Y N1 -), 3、 -Y N2 -Y N1 -(Y N2 -Y N1 -), 3、 -Y N2 -(Y N1 -Y N2 -Y N1 -), 3; etc. can be mentioned.

[0116] Y N Preferred examples of -Y N1 -,-Y N1 -Y N2 -,-Y N1 -Y N2 -Y N1 -,-Y N1 -Y N2 (-)2, -Y N2 -,-Y N2 -Y N1 -,-Y N2 -Y N1 -Y N2 -,-Y N2 -Y N1 (-)2, etc. In the amine-modified product, one or more Ys N preferably have a -(C=O)- at the terminal side of the amine skeleton and are preferably bonded to the nitrogen atom in the amine skeleton.

[0117] Y N is preferably -Y N1 -,-Y N1 -Y N2 -,-Y N1 -Y N2 -Y N1 -,-Y N1 -Y N2 (-)2, -Y N2 -,-Y N2 -Y N1 -,-Y N2 -Y N1 -Y N2 -,-Y N2 -Y N1 (-)2, [In the formula, Y N1 is, in each occurrence, independently 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-、 or -C(=O)-NR’- -C(=O)-NR’-C(=O)- (In the formula, R’ is, independently at each occurrence, a hydrogen atom or a hydrocarbon 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).) is, Y N2 is a divalent to tetravalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, or a divalent aromatic group (for example, a divalent phenyl group, a divalent triazole group).] a group represented by this. Thereby, liquid repellency can be imparted to the substrate well.

[0118] Y N As further specific examples of *-(C=O)- -O-(C=O)-NR’- [In the formula, * means being bonded to the nitrogen atom of the amine skeleton, R’ is a hydrogen atom or a hydrocarbon 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).] etc. can be mentioned.

[0119] (Z N ) Z N is a monovalent hydrocarbon group having 6 or more and 40 or less carbon atoms which may have a substituent, and the description in the above (monovalent hydrocarbon group which may have a substituent) is incorporated herein.

[0120] [Examples of amine-modified products] (Amine-modified product example 1) As an example of an amine-modified product, the following formula: N(-Y N -Z N n ) p (-H) q -L 1 -[N(-YN -Z N n ) r (-H) s -L 1 -] t -N(-Y N -Z N n ) p (-H) q [wherein Y N is, independently at each occurrence, a direct bond or a 1 + n-valent group, Z N is, independently at each occurrence, a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, L 1 is, independently at each occurrence, a divalent aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms which may be interrupted by an oxygen atom and / or a sulfur atom, n is, independently at each occurrence, an integer of 1 or more and 3 or less, p is, independently at each occurrence, an integer of 0 or more and 2 or less, q is, independently at each occurrence, an integer of 0 or more and 2 or less, p + q is 2 in each N(-Y N -Z N n ) p (-H) q and is 2, r is, independently at each occurrence, 0 or 1, s is, independently at each occurrence, 0 or 1, r + s is 1 in each N(-Y N -Z N n ) r (-H) s and is 1, the sum of all p and all r is 1 or more, t is an integer of 0 or more and 10 or less.] Examples thereof include the compound represented by (amine-modified example 1).

[0121] In amine-modified example 1, YN , Z N For details of Z and n, refer to the above description.

[0122] In amine modification system 1, L 1 is a divalent aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms, which may be interrupted by an oxygen atom and / or a sulfur atom, and may be a cyclic, branched, or linear hydrocarbon group, preferably a chain hydrocarbon group or an aromatic hydrocarbon. L 1 may refer to the hydrocarbon groups in the description of the [amine skeleton] mentioned above. The hydrocarbon group may be interrupted by an oxygen atom and / or a sulfur atom, or may consist only of carbon atoms, nitrogen atoms, and hydrogen atoms. L 1 For example, it may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 hydrocarbon aromatic rings. L 1 Preferably, L is a cyclic group having both a ring (e.g., aromatic ring) and a chain structure (e.g., linear structure, ether oxygen, thioether sulfur). Specific examples include 1,3-phenylenebisalkylene group, 1,4-phenylenebisalkylene group, diphenyl ether diyl group, diphenyl thioether diyl group, etc. L 1 The carbon number of L may be 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more, and may also be 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, or 3 or less.

[0123] In amine modification system 1, p is, independently at each occurrence, an integer of 0 or more and 2 or less, q is, independently at each occurrence, an integer of 0 or more and 2 or less, and p + q is 2 in each N(-Y N -Z N n ). p (-H) q Preferably, p may be 1 or more, for example 2, independently at each occurrence.

[0124] In amine modification form 1, r is independently 0 or 1 at each occurrence, s is independently 0 or 1 at each occurrence, and r + s is 1 in each N(-Y N -Z N n ) r (-H) s . Preferably, p can be independently 1 or more at each occurrence, for example, 2.

[0125] The sum of all p and all r is 1 or more. That is, amine modification form 1 has one or more -Y N -Z N n . The sum of all p and all r can be 1 or more, 3 or more, 5 or more, 7 or more, 9 or more, 12 or more (the sum of all q and all s can be 0), 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, or 4 or less.

[0126] In amine modification form 1, t is an integer from 0 to 10. t can be 0 or more, 1 or more, 2 or more, 4 or more, or 6 or more, preferably 0 or more or 2 or more, and t can be 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1 or less, for example, 0 or 1.

[0127] (Amine modification form 2) As an example of other amine modification forms, the following formula: N(-Y N -Z N n ) p (-H) q -L 2 (-Y N -Z N n ) u [In the formula, Y N is, independently at each occurrence, a direct bond or a (1 + n)-valent group, Z N is, independently at each occurrence, a linear or branched monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, L2 is an aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 + u valences and 2 to 20 carbon atoms, which may be interrupted by an oxygen atom and / or a sulfur atom, n is, independently in each occurrence, an integer of 1 or more and 3 or less, p is an integer of 0 or more and 2 or less, q is an integer of 0 or more and 2 or less, p + q is 2, u is an integer of 1 or more and 3 or less, The sum of p and u is 1 or more.] Examples thereof include compounds represented by (amine modification example 2).

[0128] In amine modification example 2, Y N , Z N For details of and n, the above description is incorporated by reference.

[0129] In amine modification example 2, L 2 is an aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 + u valences and 2 to 20 carbon atoms, which may be interrupted by an oxygen atom and / or a sulfur atom, and may be a cyclic, branched, or linear hydrocarbon group, preferably a chain hydrocarbon group or an aromatic hydrocarbon. L 2 As L, the hydrocarbon groups in the above description of [amine skeleton] may be incorporated by reference. The hydrocarbon group may be interrupted by an oxygen atom and / or a sulfur atom, or may consist only of carbon atoms, nitrogen atoms, and hydrogen atoms. L 2 is, for example, a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 hydrocarbon aromatic rings. L 2 is preferably a cyclic group having a ring (e.g., aromatic ring) and a chain structure (e.g., linear structure, ether oxygen, thioether sulfur). Specific examples include 1,3-phenylene bisalkylene group, 1,4-phenylene bisalkylene group, diphenyl ether diyl group, diphenyl thioether diyl group, etc. L 2The carbon number may be 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more, and may be 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, or 3 or less.

[0130] In amine modification form 2, p is an integer of 0 or more and 2 or less, q is an integer of 0 or more and 2 or less, and p + q is 2. Preferably, p may be 1 or more, for example, 2.

[0131] In amine modification form 2, u is an integer of 1 or more and 3 or less. u is 1, 2, or 3, for example, 2 or 3.

[0132] In amine modification form 2, the sum of p and u is 1 or more, that is, amine modification form 2 has one or more -Y N -Z N n and has. The sum of all p and u may be 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more (the sum of all q may be 0), and the sum of p and u may be 5 or less, 4 or less, 3 or less, or 2 or less.

[0133] (Specific example) As a specific example of the amine-modified body, a compound represented by the following formula can be mentioned. Regarding the details of Z in the following formula, the above description Z N is cited.

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[0141] The amine-modified product may be a synthetic wax derived from animal and vegetable fats and oils. The synthetic wax may be obtained by condensing a fatty acid derived from animal and vegetable fats and oils with an aliphatic amine or an amine containing an aromatic group. Examples of the synthetic wax include fatty acid amide compounds such as hydroxy fatty acid amide compounds, palmitic acid amide compounds, octadecanoic acid amide compounds, stearic acid amide compounds, arachidic acid amide compounds, behenic acid amide compounds, lignoceric acid amide compounds, oleic acid amide compounds, linoleic acid amide compounds, α-linolenic acid amide compounds, γ-linolenic acid amide compounds, arachidonic acid amide compounds, eicosapentaenoic acid amide compounds, and docosahexaenoic acid amide compounds.

[0142] [Manufacturing method] Examples of the method for producing the amine-modified product include, but are not limited to, a method of synthesizing by reacting a Z N group-containing carboxylic acid with various amines (raw material amines) in the presence of a condensing agent if necessary, and a method of synthesizing by reacting acid chlorides, acid anhydrides, isocyanates, etc. of carboxylic acids containing a Z N group with various amines. The condensing agent may be a known condensing agent, and examples thereof include DCC, EDCI, CDI, BOP, COMU, DMT-MM, DPPA, Py-Bop, etc.

[0143] (Amine (raw material amine)) Examples of amines (raw material amines) that are precursors of amine skeletons include alkylamines such as methylamine, ethylamine, propylamine, butylamine, and dibutylamine, which can form amine skeletons; alkylene diamines such as ethylenediamine, propylenediamine, butylenediamine, pentanediamine, hexamethylenediamine, cyclohexanediamine, and methylenebiscyclohexylamine; polyalkylene polyamines such as diethylenetriamine, triethylenetetramine, tris(2-aminoethyl)amine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tris(2-aminopropyl)amine, tetrapropylenetetramine, pentapropylenehexamine, iminobispropylamine, dibutylenetriamine, bis(2-aminoethoxy)ethane, bis(2-aminoethyl)ether, bis[2-(2-aminoethoxy)ethyl]ether, bis[2-(3-aminopropoxy)ethyl]ether, spermine, and spermidine; oxygen- or sulfur-containing aliphatic amines such as 1-aminopropanediol, 2-amino-1,3-propanediol, 3-amino-1,2-propanediol, polyoxypropylenediamine, and polyoxyethylenediamine; aromatic monoamines such as aniline, 1- or 2-naphthylamine, 1-, 2-, or 9-aminoanthracene, 9-aminophenanthrene, and 2-, 3-, or 4-aminobiphenyl; monocyclic aromatic polyamines such as o-, m-, or p-phenylenediamine, o-, m-, or p-xylylenediamine, diaminotoluene, 2,3-, 2,4-, or 2,5-tolylenediamine;Polycyclic aromatic polyamines such as diaminobiphenyl, bisaminophenoxyphenylpropane, diaminodiphenyl ether, diaminodiphenyl sulfide, diaminodiphenyl sulfone, diaminobenzophenone, diaminodiphenylmethane, diaminophenylpropane, diaminophenylhexafluoropropane, diaminophenylphenylethane, bisaminophenoxybenzene, bisaminobenzoylbenzene, bisaminodimethylbenzylbenzene, aminophenoxybiphenyl, aminophenoxyphenyl ketone, bisaminoditrifluoromethylbenzylbenzene, aminophenoxyphenyl sulfone, aminophenoxyphenyl ether, aminophenoxyphenylpropane, bis(aminophenoxybenzoyl)benzene, bis(aminophenoxy-α,α-dimethylbenzyl)benzene, bis[(aminoaryloxy)benzoyl]diphenyl ether, bis(amino-α,α-dimethylbenzylphenoxy)benzophenone, aminophenoxyphenyl sulfide, bis[amino-α,α-dimethylbenzylphenoxy]diphenyl sulfone, 4,4'-bis[aminophenoxyphenoxy]diphenyl sulfone, diaminodiaryloxybenzophenone, diaminoaryloxybenzophenone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diaminotriphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-methylenebisaniline, 4,4'-oxydianiline, 1,3-bis(4-aminophenoxy)benzene, 4,4'-diaminodiphenyl ether, 4,4'-bis(aminophenyl)amine; oxygen- or sulfur-containing polycyclic aromatic polyamines such as 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, etc.;2-Hydroxyethyl ethylenediamine, 2-hydroxyethyl propylenediamine, di-2-hydroxyethyl ethylenediamine, di-2-hydroxyethyl propylenediamine, 2-hydroxypropyl ethylenediamine, di-2-hydroxypropyl ethylenediamine, and other hydroxyl group-containing polyamines may be mentioned. The polyamine may be a polymer obtained by polymerizing a polymerizable compound such as allylamine.;

[0144] [Polyol-modified product] As an example of the liquid-repellent compound, the polyol-modified product will be described. The polyol-modified product is a compound obtained by chemically modifying a polyol so as to exhibit liquid repellency.

[0145] [Structure, etc.] The polyol-modified product may be a polymer having a polymerization degree of 1 or more. From the viewpoint of improving liquid repellency, the polymerization degree of the polyol-modified product may be 2 or more, 3 or more, 5 or more, 6 or more, preferably 7 or more, more preferably 8 or more, and even more preferably 9 or more. 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, and even more preferably 15 or less. The polymerization degree means the number of repeating monomer units constituting the polymer.

[0146] The polymerization degree in the present disclosure means the average polymerization degree. The average polymerization degree 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 polymerization degree of the polyol-modified product means the average polymerization degree of the above polyglycerol. The average polymerization degree of polyglycerol is the average polymerization degree (n) calculated from the hydroxyl value by the end group analysis method. Specifically, the average polymerization degree 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 indicator of the number of hydroxyl groups contained in polyglycerin. 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 polyglycerin, and is calculated in accordance with "Japanese Oil Chemists' Society Standard, Standard Oil Analysis Test Methods (I), 2003 Edition" compiled by the Japan Oil Chemists' Society. The hydroxyl value of the raw material polyglycerin is actually measured according to the above standard oil analysis test method, and the average degree of polymerization and average molecular weight of polyglycerin can be calculated from the above relational expression.

[0147] 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.

[0148] 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 performed 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, as follows. The top of the peaks of the respective analysis results obtained by ordinary analysis methods such as HPLC, GC, and HPAEC is taken as the average degree of polymerization. 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.

[0149] The polyol-modified product may be a low-molecular-weight compound (for example, having a weight-average molecular weight of less than 1500, less than 1000, or 500 or less) and / or a high-molecular-weight compound. 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.

[0150] The substitution rate of the hydroxy groups in the polyol-modified product may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 100%, preferably 10% or more, for example 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, particularly 80% or more, and may 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 6 to 40 carbon atoms that may have a substituent.

[0151] The residual ratio of the hydroxyl groups in the polyol-modified product may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, for example, it may be 5% or more. Also, it may be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, 15% or less, or 5% or less, for example, it may be 50% or less, 30% or less, or 10% or less. Here, the "residual ratio" means the unmodified ratio (mol%) among the hydroxyl groups derived from the polyol.

[0152] The number of modifying groups in the polyol-modified product may be 2 or more, 5 or more, 7 or more, 8 or more, 9 or more, 10 or more, 12 or more, 15 or more, 30 or more, or 50 or more. Also, it may be 1000 or less, 750 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less. Here, the modifying group is preferably a monovalent hydrocarbon group which may have a substituent.

[0153] The modifying group equivalent of the polyol-modified product may be 150 or more, 250 or more, 350 or more, 450 or more, 550 or more, 650 or more, 750 or more, or 1000 or more. Also, it may be 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, or 400 or less. It is the value obtained by dividing the weight average molecular weight of the polyol-modified product by the number of modifying groups. Here, the modifying group is preferably a monovalent hydrocarbon group which may have a substituent.

[0154] In the polyol-modified product, one or more hydroxyl groups of the polyol are substituted by modifying groups. The modifying group is preferably a monovalent hydrocarbon group which may have a substituent. From the viewpoint of improving liquid repellency, the polyol-modified product may have a structure in which an aliphatic hydrocarbon group having 6 to 40 carbon atoms is used to modify the polyol.

[0155] For details of the monovalent hydrocarbon group which may have a substituent, the description of (the monovalent hydrocarbon group which may have a substituent) above is incorporated by reference.

[0156] (-Y O -Z O n ) In the polyol modifier in the present disclosure, one or more hydroxy groups of the polyol are represented by the following formula: -Y O -Z O n [wherein, Y O is a 1 + n-valent group composed of one or more selected from the group consisting of Y O1 and Y O2 , Y O1 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-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2, and -N(-)2 (wherein, R' is independently, in each occurrence, a hydrogen atom or a hydrocarbon 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)). Y O2 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 and 1 to 40 carbon atoms, an optionally substituted hydrocarbon aromatic ring, and an optionally substituted heterocyclic ring. Z O is an optionally substituted monovalent hydrocarbon group having 6 to 40 carbon atoms, n is an integer of 1 or more and 3 or less. ] and may be substituted by a group represented by

[0157] (Y O ) Y O is a 1 + n-valent group composed of one or more selected from the group consisting of Y O1 and Y O2 , Y O1is a group composed of one or more selected from the group consisting of direct bond, -O-, -C(=O)-, -C(=NR’)-, -S-, -S(=O)2-, -C(=S)-, -NR’-, -C(OR’)R’-, -C(OR’)(-)2, and -N(-)2 (wherein R’ is, in each occurrence, independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20, 1 to 10, or 1 to 4 carbon atoms).). Y O2 is a group composed of one or more selected from the group consisting of an optionally substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms and 2 to 4 valences, an optionally substituted hydrocarbon aromatic ring, and an optionally substituted heterocyclic ring having 2 to 4 valences.

[0158] n is the number of O Z that binds to Y O 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.

[0159] Y O The molecular weight of may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more, and may 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.

[0160] Y O may contain at least an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfonamide group, a sulfourea group, a sulfourethane group, or a sulfonimide group. For example, Y O may contain -C(=O)-NR’-, -C(=S)-NR’-, -O-C(=O)-NR’-, -NR’-C(=O)-, -NR’-C(=O)-NR’-, or -SO2NR’-. Y O By Y containing these groups, the liquid repellency can be improved.

[0161] ○ Y O1 Y O1 is a non-hydrocarbon linker.

[0162] Y O1 is a direct bond or a polyvalent group. Y O1 The valence of Y may be 2 to 4, 2 to 3, or 2. Y O1 It is preferably not only a direct bond.

[0163] Y O1 The molecular weight of Y may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0164] Y O1 is composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -S(=O)2-, -NR’-, -C(OR’)R’-, and -C(OR’)(-)2 (wherein R’ is, in each occurrence, independently a hydrogen atom or a hydrocarbon 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)). Y O1 Examples of Y 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’-, -SO2-, -SO2NR’-, -C(OR’)R’-, -C(OR’)(-)2, etc. (wherein R’ is, in each occurrence, independently a hydrogen atom or a hydrocarbon 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).) include the following.

[0165] Y O1 may contain at least an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfonamide group, a sulfonylurea group, a sulfonylurethane group, or a sulfonimide group. For example, Y O2 may contain -C(=O)-NR’-, -O-C(=O)-NR’-, -NR’-C(=O)-, -NR’-C(=O)-NR’-, or -SO2NR’-. Y O1 By containing these groups, the liquid repellency can be improved.

[0166] ○ Y O2 Y O2 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.

[0167] Y O2 may be a hydrocarbon group or a non-hydrocarbon group (including a heteroatom). Y O2 may be aliphatic or aromatic. Y O2 may be linear, branched, or cyclic.

[0168] Y O2 is a group with a valence of two or more. Y O2 The valence of may be, for example, 2 to 4, 2 to 3, or 2.

[0169] Y O2 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 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.

[0170] Y O2It is 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.

[0171] The divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched-chain, or straight-chain hydrocarbon group. The divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The number of carbon atoms of the aliphatic hydrocarbon group having 1 to 40 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more, and may 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.

[0172] The aliphatic hydrocarbon group may have a substituent. Examples of the substituent include -OR’, -N(R’)2, -COOR’, and a halogen atom, etc. (wherein, R’ is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have an active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the 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.

[0173] 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.

[0174] The hydrocarbon aromatic ring may have a substituent. Examples of the substituent include -R’, -OR’, -N(R’)2, -COOR’, and a halogen atom, etc. (wherein, R’ is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have an active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the 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.

[0175] The divalent to tetravalent heterocyclic rings may be aliphatic groups or aromatic groups. Examples of the divalent to tetravalent heterocyclic rings 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.

[0176] The heterocyclic ring may have a substituent. Examples of the substituent include -R’, -OR’, -N(R’)2, -COOR’, and a halogen atom, etc. (wherein, R’ is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have an active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the 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.

[0177] Y O2 Examples of -Ali- -Cy- -Ali(-)2 -Cy(-)2 (-)2Ali- (-)2Cy- (-)2Ali(-)2 (-)2Cy(-)2 -Ali-Cy- -Cy-Ali- -Cy-Ali-Cy- -Ali-Cy-Ali- [In the formula, Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and Cy is a hydrocarbon aromatic ring or a heterocyclic ring.] etc. can be mentioned.

[0178] Y O2 Specific examples of -(CH2) p -(p is from 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, -(CH2) q -Cy-(CH2) r -(q and r are each independently from 0 to 20, for example 1 to 10, and Cy is a hydrocarbon aromatic ring or a heterocyclic ring) etc. can be mentioned.

[0179] (Y O example) Y O Examples of will be described. In the following, R’ is, in each occurrence, independently, a hydrogen atom or a hydrocarbon group having 1 to 30 (for example 1 to 20, 1 to 10, or 1 to 4) carbon atoms.

[0180] Y O Examples of are, when Y O is divalent, -Y O1 -, -Y O1 -Y O2 -, -Y O1 -Y O2 -Y O1 -, -Y O1 -Y O2 -Y O1 -Y O2 -, -Y O2 -, -Y O2 -Y O1 -, -YO2 -Y O1 -Y O2 -、-Y O2 -Y O1 -Y O2 -Y O1 - etc. can be mentioned.

[0181] Y O As an example of Y O when Y is trivalent, -Y O1 (-)2, -Y O1 -Y O2 (-)2, -Y O1 -(Y O2 -)2, -Y O1 -Y O2 -Y O1 (-)2, -Y O1 -Y O2 (-Y O1 -)2, -Y O1 -(Y O2 -Y O1 -)2, -Y O1 -Y O2 -Y O1 -Y O2 (-)2, -Y O1 -Y O2 -Y O1 -(Y O2 -) 2、 -Y O1 -Y O2 -(Y O1 -Y O2 -) 2、 -Y O1 -(Y O2 -Y O1 -Y O2 -)2; -Y O2 (-)2, -Y O2 -Y O1 (-)2, -Y O2 -(Y O1 -)2, -Y O2 -Y O1 -Y O2 (-)2, -Y O2 -Y O1 (-Y O2 -)2, -Y O2 -(Y O1 -Y O2 -)2, -Y O2 -Y O1 -YO2 -Y O1 (-)2, -Y O2 -Y O1 -Y O2 -(Y O1 -) 2、 -Y O2 -Y O1 -(Y O2 -Y O1 -) 2、 -Y O2 -(Y O1 -Y O2 -Y O1 -)2, etc. can be mentioned.

[0182] Y O As an example of Y O when it is tetravalent, -Y O1 (-)3, -Y O1 -Y O2 (-)3, -Y O1 -(Y O2 -)3, -Y O1 -Y O2 -Y O1 (-)3, -Y O1 -Y O2 (-Y O1 -)3, -Y O1 -(Y O2 -Y O1 -)3, -Y O1 -Y O2 -Y O1 -Y O2 (-)3, -Y O1 -Y O2 -Y O1 -(Y O2 -) 3、 -Y O1 -Y O2 -(Y O1 -Y O2 -) 3、 -Y O1 -(Y O2 -Y O1 -Y O2 -)3; -Y O2 (-)3, -Y O2 -Y O1 (-)3, -Y O2 -(Y O1 -)3, -Y O2 -Y O1 -YO2 (-)3, -Y O2 -Y O1 (-Y O2 -)3, -Y O2 -(Y O1 -Y O2 -)3, -Y O2 -Y O1 -Y O2 -Y O1 (-)3, -Y O2 -Y O1 -Y O2 -(Y O1 -) 3、 -Y O2 -Y O1 -(Y O2 -Y O1 -) 3、 -Y O2 -(Y O1 -Y O2 -Y O1 -)3; etc. can be mentioned.

[0183] Y O Preferred examples of -Y O1 -, -Y O1 -Y O2 -, -Y O1 -Y O2 -Y O1 -, -Y O1 -Y O2 (-)2, -Y O2 -, -Y O2 -Y O1 -, -Y O2 -Y O1 -Y O2 -, -Y O2 -Y O1 (-)2, etc. can be mentioned.

[0184] (Preferred Y O example) Preferably, Y O is -O-Y O11 -, or -O-Y O11 -Y O21 -Y O12 - [In the formula, each symbol is independent at each occurrence, Y O11 is a direct bond, -C(=O)-, -C(=O)-NR’-, or -C(=S)-NR’-. Y O21 is a hydrocarbon group having 1 to 40 carbon atoms. Y O12 is -O-, -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’-, -SO2-, -SO2NR’-, -C(OR’)R’-, or -C(OR’)(-)2.], may be.

[0185] Y O11 is a non-hydrocarbon linker, which is a direct bond or a polyvalent group.

[0186] Y O11 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.

[0187] Y O11 may be a direct bond, -C(=O)-, -C(=O)-NR’-, or -C(=S)-NR’-.

[0188] Y O21 is a divalent hydrocarbon linker and may be a hydrocarbon group having 1 to 40 carbon atoms.

[0189] Y O21 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.

[0190] Here, the hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or straight-chain hydrocarbon group, and may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group.

[0191] Y O21 Specific examples of -(CH2) 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, -(CH2) q -Cy-(CH2) 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 can be mentioned.

[0192] Y O12 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’-, -SO2-, -SO2NR’-, -C(OR’)R’-, or -C(OR’)(-)2.

[0193] Y O12 may at least contain an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfonamide group, a sulfourea group, a sulfourethane group, or a sulfonimide group. For example, Y O12 may be -C(=O)-NR’-, -O-C(=O)-NR’-, -NR’-C(=O)-, -NR’-C(=O)-NR’- or -SO2NR’-. Y C12 By Y containing these groups, the liquid repellency can be improved.

[0194] (Z O ) ZO is a monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, and the description in the above (monovalent hydrocarbon group which may have a substituent) is incorporated herein by reference.

[0195] [Other modifying groups] The hydroxy group of the polyol is -Y O -Z O n may be substituted with a modifying group other than the above. Examples of the modifying group are an anionic group and / or a cationic group.

[0196] Examples of the anionic group include monomers having a carboxyl group, a sulfonic acid group, or a phosphoric acid group.

[0197] Examples of the salt of the anionic group include an alkali metal salt, an alkaline earth metal salt, or an ammonium salt, such as a methylammonium salt, an ethanolammonium salt, a triethanolammonium salt, and the like.

[0198] Examples of the cationic group include an amino group, preferably a tertiary amino group and a quaternary amino group. In the tertiary amino group, the two groups bonded to the nitrogen atom are the same or different and are preferably 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 (C6H5-CH2-)). In the quaternary amino group, the three groups bonded to the nitrogen atom are the same or different and are preferably 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 (C6H5-CH2-)). 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.

[0199] The cationic group which is a salt is a salt with an acid (organic acid or inorganic acid). Organic acids, for example, carboxylic acids having 1 to 20 carbon atoms (particularly monocarboxylic acids such as acetic acid, propionic acid, butyric acid, stearic acid, etc.) are preferred.

[0200] [Production method] The polyol-modified product may be produced by reacting a modifier having a modifying group (or a precursor structure of the modifying group) with a hydroxy group of the polyol.

[0201] (Polyol) The polyol is a compound having two or more hydroxy groups and is a compound serving as a raw material for the polyol-modified product. The polyol is a compound having two or more hydroxy groups in the molecule. The polyol may be aliphatic or aromatic, but is preferably aliphatic.

[0202] 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.

[0203] When the polyol is a polymer, it may have a hydroxy group and an ether bond in the repeating structure of the monomer unit.

[0204] 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.

[0205] The number of hydroxy groups in the polyol may be 2 or more, 5 or more, 7 or more, 10 or more, 15 or more, 30 or more, 50 or more, or 100 or more, and may 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.

[0206] The hydroxy group equivalent of the polyol may be 20 or more, 40 or more, 60 or more, 80 or more, 100 or more, 120 or more, or 150 or more, and may 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 group equivalent of the polyol is the value obtained by dividing the weight average molecular weight of the polyol by the number of hydroxy groups.

[0207] 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. Compounds converted from microorganisms are also included among the above natural products. 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.

[0208] Examples of the monosaccharides include glucose, fructose, galactose, xylose, and the like.

[0209] Examples of the oligosaccharides include sucrose, cycloamylose, cyclodextrin, maltose, trehalose, lactose, sucralose, and the like.

[0210] Examples of the sugar alcohols (reducing sugars) include sorbitol, maltitol, erythritol, isomalt, lactitol, mannitol, xylitol, sorbitan, lactitol, and the like.

[0211] Examples of 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.

[0212] Examples of hydroxy acids include ascorbic acid, kojic acid, quinic acid, chlorogenic acid, gluconic acid, etc.

[0213] Examples of amino acids include glucosamine, etc.

[0214] Examples of vitamins include ascorbic acid, inositol, etc.

[0215] Examples of flavonols include catechin, quercetin, anthocyanin, etc.

[0216] Examples of hydroxyhydrocarbons include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, glycerin, trimethylolpropane, trimethylolethane, etc. 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 included in other groups such as polysaccharides (other hydroxyhydrocarbons).

[0217] Examples of hydroxy group-containing compound polymers include polyglycerin, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymer, hydroxypropyl (meth)acrylate polymer, hydroxybutyl (meth)acrylate polymer, etc.

[0218] 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.

[0219] 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.

[0220] Examples of the polyester polyol may be compounds obtained by dehydrative condensation of a compound having two or more carboxyl groups and a compound having two or more hydroxyl groups. Examples of the compound having two or more carboxyl groups include terephthalic acid, isophthalic acid, phthalic acid, methylphthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, succinic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, and acid anhydrides thereof. Examples of the compound having two or more hydroxyl groups include ethylene glycol, propylene glycol, propanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and polymers thereof.

[0221] (Modifier) The modifier is a compound having reactivity with the polyol, and is preferably a compound having a monovalent hydrocarbon group having 6 or more and 40 or less carbon atoms which may have a substituent as described above.

[0222] Examples of the modifier are as follows. Acid halide G(O=)C-Z O Acid anhydride O(C(=O)-Z O )2 Carboxylic acid HO(O=)C-Z O Isocyanate O=C=N-Z O Thiocyanate S=C=N-Z O Epoxy (CH2OCH)CH2O-Z O Halide G-Z O Amine H2N-Z O Hydroxy HO-Z O [In the formula, Z O is as described above, and G is a halogen atom (for example, F, Cl, Br, or I).]

[0223] Z in the structure of the above modifier O may be replaced with any group constituting the modifying group. For example, Z O may be a monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent. For example, Z O may be -Y O -Z O n and so on.

[0224] The polyol-modified product 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 the hydroxy group of the polyol to form an ester bond, thereby synthesizing a polyol-modified product. Further, a modifier which is a halide or an epoxy compound is reacted with the hydroxy group of the polyol to form an ether bond, thereby generating a polyol-modified product. Those skilled in the art can appropriately design the reaction conditions between the polyol and the modifier, such as the use of a catalyst (e.g., an acid catalyst or a base catalyst) and the use of a condensing agent, according to the target product.

[0225] [Polycarboxylic acid-modified product] As an example of the liquid-repellent compound, a polycarboxylic acid-modified product will be described. The polyol-modified product is a compound obtained by chemically modifying so as to exhibit liquid repellency with respect to the polycarboxylic acid-modified product.

[0226] [Structure, etc.] The polycarboxylic acid-modified product may be a low molecular weight (e.g., weight average molecular weight less than 1500, less than 1000, 500 or less) and / or a high molecular weight. The weight average molecular weight of the polycarboxylic acid-modified product may be 100 or more, 200 or more, 300 or more, 400 or more, 500 or more, 1000 or more, 3000 or more, 5000 or more, 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.

[0227] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polycarboxylic acid-modified product may be values measured by GFC analysis using polyethylene glycol / polyethylene oxide as a standard sample under the following apparatus and conditions. Separation column: SB-806M (8 mm × 30 mm, Shodex) Column temperature: 40 °C Mobile phase solvent: Ion-exchanged water Mobile phase flow rate: 1.0 mL / min Sample concentration: 0.5 wt% Injection volume: 50 μL Detector: RI detector (Waters2414, Waters)

[0228] The weight average molecular weight (Mw), number average molecular weight (Mn), and polydispersity (Mw / Mn) of the polycarboxylic acid-modified product in terms of polystyrene may be determined by gel permeation chromatography (GPC) measurement using tetrahydrofuran (THF) as an eluent and Shodex °KF400RL and KF400RH columns (polystyrene gel) manufactured by Showa Denko KK.

[0229] The substitution rate of the carboxyl group's hydroxyl group in the polycarboxylic acid modified product may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 100%, preferably 10% or more, for example 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, particularly 80% or more, and may also be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, 15% or less, for example 95% or less. Here, the "substitution rate" means the proportion (mol%) of the hydroxyl groups of the carboxyl groups derived from the polycarboxylic acid that are modified, and may mean the proportion (mol%) modified by a monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent.

[0230] The remaining rate of the carboxyl group's hydroxyl group in the polycarboxylic acid modified product may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, for example 5% or more, 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 "remaining rate" means the proportion (mol%) of the hydroxyl groups of the carboxyl groups derived from the polycarboxylic acid that are not modified.

[0231] The number of modifying groups possessed by the polycarboxylic acid modified product may be 2 or more, 5 or more, 7 or more, 10 or more, 15 or more, 30 or more, or 50 or more, and may 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 which may have a substituent.

[0232] The equivalent weight of the modifying group of the polycarboxylic acid modifier 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 polycarboxylic acid modifier by the number of modifying groups. Here, the modifying group is preferably a monovalent hydrocarbon group which may have a substituent.

[0233] In the polycarboxylic acid modifier, one or more hydroxy groups of the polycarboxylic acid are substituted by a modifying group. The modifying group is preferably a monovalent hydrocarbon group which may have a substituent. From the viewpoint of improving liquid repellency, the polycarboxylic acid modifier may have an aliphatic hydrocarbon group having 6 to 40 carbon atoms with respect to the polycarboxylic acid.

[0234] For the details of the monovalent hydrocarbon group which may have a substituent, the description of (the monovalent hydrocarbon group which may have a substituent) described above is incorporated by reference.

[0235] (-Y C -Z C n ) In the polycarboxylic acid modifier in the present disclosure, the hydroxy group of one or more carboxyl groups of the polycarboxylic acid has the following formula: -Y C -Z C n [wherein, Y C is a 1 + n-valent group composed of one or more selected from the group consisting of Y C1 and Y C2 , Y C1is a group composed of one or more selected from the group consisting of direct bond, -O-, -C(=O)-, -C(=NR’)-, -S-, -S(=O)2-, -C(=S)-, -NR’-, -C(OR’)R’-, -C(OR’)(-)2, and -N(-)2 (wherein R’ is, in each occurrence, independently a hydrogen atom or a hydrocarbon 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)). Y C2 is a group composed of one or more selected from the group consisting of an optionally substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms and 2 to 4 valences, an optionally substituted hydrocarbon aromatic ring having 2 to 4 valences, and an optionally substituted heterocyclic ring having 2 to 4 valences. Z C is an optionally substituted monovalent hydrocarbon group having 6 to 40 carbon atoms. n is an integer of 1 or more and 3 or less.] may be substituted by a group represented by.

[0236] (Y C ) Y C is Y C1 and Y C2 is a (1 + n)-valent group composed of one or more selected from the group consisting of. Y C1 is a group composed of one or more selected from the group consisting of direct bond, -O-, -C(=O)-, -C(=NR’)-, -S-, -S(=O)2-, -C(=S)-, -NR’-, -C(OR’)R’-, -C(OR’)(-)2, and -N(-)2 (wherein R’ is, in each occurrence, independently a hydrogen atom or a hydrocarbon 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)). Y C2 is a group composed of one or more selected from the group consisting of an optionally substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms and 2 to 4 valences, an optionally substituted hydrocarbon aromatic ring having 2 to 4 valences, and an optionally substituted heterocyclic ring having 2 to 4 valences.

[0237] n is Y C bonded to Z Cis a number and may be an integer of 1 or more and 3 or less. n may be 1 or more, 2 or more, or 3 or more. n may be 3 or less, 2 or less, or 1 or less, for example, 2 or less.

[0238] Y C The molecular weight of may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more, and may 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.

[0239] Y C may contain at least an amide group, urethane group, urea group, imide group, thioamide group, thiourethane group, thiourea group, thioimide group, sulfonamide group, sulfoneurea group, sulfoneurethane group, or sulfonimide group. For example, Y C may be -C(=O)-NR’-, -O-C(=O)-NR’-, -NR’-C(=O)-, -NR’-C(=O)-NR’- or -SO2NR’-. Y C By Y containing these groups, the liquid repellency can be improved.

[0240] ○ Y C1 Y C1 is a non-hydrocarbon linker.

[0241] Y C1 is a direct bond or a divalent or higher group. Y C1 The valence of may be 2 to 4, 2 to 3, or 2. Y C1 It is preferably not only a direct bond.

[0242] Y C1 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.

[0243] Y C1may be composed of one or more selected from the group consisting of 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 a hydrocarbon 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)). Y C1 Examples of 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’-, -SO2-, -SO2NR’-, -C(OR’)R’-, -C(OR’)(-)2 etc. (wherein R’ is, independently at each occurrence, a hydrogen atom or a hydrocarbon 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).) include.

[0244] Y C1 may contain at least an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfonamide group, a sulfourea group, a sulfourethane group, or a sulfonimide group. For example, Y C1 may contain -C(=O)-NR’-, -O-C(=O)-NR’-, -NR’-C(=O)-, -NR’-C(=O)-NR’- or -SO2NR’-. Y C1 By containing these groups, the liquid repellency can be improved.

[0245] ○ Y C2 YC2 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.

[0246] Y C2 may be a hydrocarbon group or a non-hydrocarbon group (including a heteroatom). Y C2 may be aliphatic or aromatic. Y C2 may be linear, branched, or cyclic.

[0247] Y C2 is a group with a valence of two or more. Y C2 The valence of may be, for example, 2 to 4, 2 to 3, or 2.

[0248] Y C2 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.

[0249] Y C2 is composed of one or more selected from the group consisting of a 2- to 4-valent aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a 2- to 4-valent hydrocarbon aromatic ring which may have a substituent, and a 2- to 4-valent heterocycle which may have a substituent.

[0250] The 2- to 4-valent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or linear hydrocarbon group. The 2- to 4-valent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The number of carbon atoms of the aliphatic hydrocarbon group having 1 to 40 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more, and may 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.

[0251] The aliphatic hydrocarbon group may have a substituent. 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 a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have an active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the 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.

[0252] Examples of the 2- to 4-valent hydrocarbon aromatic ring 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 also be 4 or less, 3 or less, or 2.

[0253] The hydrocarbon aromatic ring may have substituents. Examples of the substituents include -R’, -OR’, -N(R’)2, -COOR’, and halogen atoms, etc. (wherein, R’ is independently, in each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituents may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the hydrocarbon aromatic ring having substituents, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0254] The 2- to 4-valent heterocyclic ring may be an aliphatic group or an aromatic group. Examples of the 2- to 4-valent 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 also be 4 or less, 3 or less, or 2.

[0255] The heterocycle may have substituents. Examples of the substituents include -R’, -OR’, -N(R’)2, -COOR’, and a halogen atom, etc. (wherein R’ is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituents may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the heterocycle having substituents, 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.

[0256] Y C2 Examples of -Ali- -Cy- -Ali(-)2 -Cy(-)2 (-)2Ali- (-)2Cy- (-)2Ali(-)2 (-)2Cy(-)2 -Ali-Cy- -Cy-Ali- -Cy-Ali-Cy- -Ali-Cy-Ali- [wherein, Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and Cy is a hydrocarbon aromatic ring or a heterocycle.] etc. are included.

[0257] Y C2 Specific examples of -(CH2) p -(p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having an unsaturated bond having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, a hydrocarbon group having a branched structure having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH2) q -Cy-(CH2) 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) and the like can be mentioned.

[0258] (Y C example) Y C Examples of Y will be described. In the following, R’ is, in each occurrence, independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20, 1 to 10, or 1 to 4 carbon atoms).

[0259] Y C Examples of Y include, when Y C is divalent, -Y C1 -, -Y C1 -Y C2 -, -Y C1 -Y C2 -Y C1 -, -Y C1 -Y C2 -Y C1 -Y C2 -, -Y C2 -, -Y C2 -Y C1 -, -Y C2 -Y C1 -Y C2 -, -Y C2 -Y C1 -Y C2 -Y C1 - and the like can be mentioned.

[0260] Y C Examples of Y include, when Y C is trivalent, -Y C1 (-)2, -Y C1 -Y C2 (-)2, -Y C1 -(Y C2 -)2, -Y C1 -Y C2 -Y C1 (-)2, -Y C1 -Y C2 (-Y C1 -)2, -Y C1 -(Y C2 -YC1 -), 2, -Y C1 -Y C2 -Y C1 -Y C2 (-), 2, -Y C1 -Y C2 -Y C1 -(Y C2 -) 2、 -Y C1 -Y C2 -(Y C1 -Y C2 -) 2、 -Y C1 -(Y C2 -Y C1 -Y C2 -), 2; -Y C2 (-), 2, -Y C2 -Y C1 (-), 2, -Y C2 -(Y C1 (-), 2, -Y C2 -Y C1 -Y C2 (-), 2, -Y C2 -Y C1 (-Y C2 (-), 2, -Y C2 -(Y C1 -Y C2 (-), 2, -Y C2 -Y C1 -Y C2 -Y C1 (-), 2, -Y C2 -Y C1 -Y C2 -(Y C1 -) 2、 -Y C2 -Y C1 -(Y C2 -Y C1 -) 2、 -Y C2 -(Y C1 -Y C2 -Y C1 Examples include -), 2, etc.

[0261] Y C As an example of Y C when it is tetravalent, -Y C1 (-), 3, -Y C1 -Y C2 (-), 3, -Y C1 -(YC2 -), 3, -Y C1 -Y C2 -Y C1 (-), 3, -Y C1 -Y C2 (-Y C1 (-), 3, -Y C1 -(Y C2 -Y C1 (-), 3, -Y C1 -Y C2 -Y C1 -Y C2 (-), 3, -Y C1 -Y C2 -Y C1 -(Y C2 -) 3、 -Y C1 -Y C2 -(Y C1 -Y C2 -) 3、 -Y C1 -(Y C2 -Y C1 -Y C2 -), 3; -Y C2 (-), 3, -Y C2 -Y C1 (-), 3, -Y C2 -(Y C1 (-), 3, -Y C2 -Y C1 -Y C2 (-), 3, -Y C2 -Y C1 (-Y C2 (-), 3, -Y C2 -(Y C1 -Y C2 (-), 3, -Y C2 -Y C1 -Y C2 -Y C1 (-), 3, -Y C2 -Y C1 -Y C2 -(Y C1 -) 3、 -Y C2 -Y C1 -(Y C2 -Y C1 -) 3、 -Y C2 -(Y C1 -Y C2 -Y C1 -), 3; etc. can be mentioned.

[0262] Y C Preferred examples of -Y C1 -,-Y C1 -Y C2 -,-Y C1 -Y C2 -Y C1 -,-Y C1 -Y C2 (-)2, -Y C2 -,-Y C2 -Y C1 -,-Y C2 -Y C1 -Y C2 -,-Y C2 -Y C1 (-)2, etc. can be mentioned.

[0263] (Preferred Y C example) Preferably, Y C is -Y C11 - or -Y C11 -Y C21 -Y C12 - [Wherein, each symbol is independent at each occurrence, Y C11 is -O- or -NR'- and Y C21 is a hydrocarbon group having 1 to 40 carbon atoms, Y C12 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'-, -SO2-, -SO2NR'-, -C(OR')R'- or -C(OR')(-)2.], may be.

[0264] Y C11 is a non-hydrocarbon linker, a direct bond or a group having a valence of two or more.

[0265] Y C11 The molecular weight of Y 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.

[0266] Y C11 may be a direct bond, -C(=O)-, -C(=O)-NR'- or -C(=S)-NR'.

[0267] Y C21 is a divalent hydrocarbon linker and may be a hydrocarbon group having 1 to 40 carbon atoms.

[0268] Y C21 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.

[0269] 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 (for example, saturated) aliphatic hydrocarbon group.

[0270] Y C21 Specific examples of Y include -(CH2) 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, -(CH2) q -Cy-(CH2) 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.

[0271] Y C12may 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’-, -SO2-, -SO2NR’-, -C(OR’)R’-, or -C(OR’)(-)2.

[0272] Y C12 may contain at least an amide group, urethane group, urea group, imide group, thioamide group, thiourethane group, thiourea group, thioimide group, sulfonamide group, sulfourea group, sulfourethane group, or sulfonimide group. For example, Y C12 may be -C(=O)-NR’-, -O-C(=O)-NR’-, -NR’-C(=O)-, -NR’-C(=O)-NR’- or -SO2NR’-. Y C12 By containing these groups, the liquid repellency can be improved.

[0273] (Z C ) Z C is a monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, and the description in the above (monovalent hydrocarbon group which may have a substituent) is incorporated herein.

[0274] [Other modifying groups] The hydroxy group of the polycarboxylic acid may be substituted with a modifying group other than -Y C -Z C n Examples of the modifying group are an anionic group and / or a cationic group. For the anionic group and / or the cationic group, the description of [Other modifying groups] in the above polyol is incorporated herein.

[0275] [Production method] The polycarboxylic acid modified product may be produced by reacting a modifying agent having a modifying group (or a precursor structure of the modifying group) with the hydroxy group of the polycarboxylic acid.

[0276] (Polycarboxylic acid) A polycarboxylic acid is a compound having two or more carboxyl groups and is a compound serving as a raw material for a polycarboxylic acid modified product. A polycarboxylic acid is a compound having two or more carboxyl groups in the molecule. The polycarboxylic acid may be aliphatic or aromatic, but is preferably aliphatic.

[0277] The polycarboxylic acid may be low molecular weight (for example, having a weight average molecular weight of less than 1000, 500 or less) and / or high molecular weight. The weight average molecular weight of the polycarboxylic acid may be 100 or more, 300 or more, 500 or more, 1000 or more, 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more, and may also be 1000000 or less, 7500000 or less, 500000 or less, 3000000 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.

[0278] The number of carboxyl groups possessed by the polycarboxylic acid may be 2 or more, 5 or more, 7 or more, 10 or more, 15 or more, 30 or more, 50 or more, or 100 or more, and may 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.

[0279] The carboxyl group equivalent of the polycarboxylic acid may be 20 or more, 40 or more, 60 or more, 80 or more, 100 or more, 120 or more, 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 carboxyl equivalent of the polycarboxylic acid is a value obtained by dividing the weight average molecular weight of the polycarboxylic acid by the number of hydroxyl groups.

[0280] The polycarboxylic acid may be a natural product. The natural product may be a high molecular weight natural product, a low molecular weight natural product or a derivative thereof. The above natural products also include compounds converted from microorganisms.

[0281] The polycarboxylic acid may be at least one selected from the group consisting of dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids, carboxyl group-containing compound polymers, and salts thereof.

[0282] The dicarboxylic acid is a compound having two carboxyl groups, and examples thereof include oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, phthalic acid, terephthalic acid, malic acid, tartaric acid, aldic acid, and salts thereof.

[0283] The tricarboxylic acid is a compound having three carboxyl groups, and examples thereof include citric acid, tricarballylic acid, t-aconitic acid, trimellitic acid, and salts thereof.

[0284] The tetracarboxylic acid is a compound having four carboxyl groups, and examples thereof include pyromellitic acid and salts thereof.

[0285] The carboxyl group-containing compound polymer is a compound having five or more carboxyl groups, and examples thereof include alginic acid, tragacanth gum, gum arabic, polyacrylic acid, polymethacrylic acid, polymaleic acid, polyaspartic acid, polyglutamic acid, hyaluronic acid, heparin, xanthan gum, gellan gum, carboxymethylcellulose alginate, galacturonic acid, mannuronic acid, and salts thereof.

[0286] (Modifier) The modifier is a compound having reactivity with the polycarboxylic acid, and it is preferably a compound having a monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent as described above.

[0287] Examples of the modifier are as follows. Epoxy (CH2OCH)CH2O-Z C Amine H2N-Z C Hydroxy HO-Z C [wherein, ZC is as described above.

[0288] Z in the structure of the above-mentioned modifier C may be replaced with any group constituting the modifying group. For example, Z C may be a monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent. For example, Z C may be -Y C -Z C n may be used.

[0289] The polycarboxylic acid modified product may be synthesized by reacting a polycarboxylic acid with a modifier. For example, a modifier which is an epoxy compound is reacted with a carboxy group of a polycarboxylic acid to form an ester bond, thereby producing a polycarboxylic acid modified product. Those skilled in the art can appropriately design the reaction conditions between the polycarboxylic acid 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.

[0290] [Dispersant] The sizing agent in the present disclosure may contain a dispersant. The dispersant may be at least one selected from an organic dispersant and an inorganic dispersant. The dispersant may be at least one selected from an anionic dispersant, a nonionic dispersant, a cationic dispersant, an amphoteric dispersant, and an inorganic dispersant.

[0291] The dispersant may be used by each of the organic dispersant and the inorganic dispersant, or may be a combination of the organic dispersant and the inorganic dispersant.

[0292] 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.

[0293] The dispersant may be non-fluorine.

[0294] [Nonionic dispersant] The dispersant may contain a nonionic dispersant. The nonionic dispersant may be a nonionic surfactant.

[0295] 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 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.

[0296] Examples of nonionic dispersants include ethers, esters, ester ethers, alkanolamides, polyols, and amine oxides.

[0297] Examples of ethers are compounds having an oxyalkylene group (preferably a polyoxyethylene group).

[0298] 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.

[0299] 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.

[0300] Examples of alkanolamides are formed from fatty acids and alkanolamines. The alkanolamide may be a monoalkanolamide or a dialkanolamine. 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.

[0301] The polyol may be an alcohol having 2 to 5 valences and 10 to 30 carbon atoms. The amine oxide may be an oxide of an amine (secondary amine or preferably tertiary amine) (e.g., having 5 to 50 carbon atoms).

[0302] 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.

[0303] 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.

[0304] 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.

[0305] The nonionic dispersant has the formula: R 1 O-(CH2CH2O) p -(R 2 O) q -R 3 [In the formula, R 1 is an alkyl group having 1 to 22 carbon atoms, 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

[0306] R 1Preferably has 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 include a propylene group and a butylene group. In the nonionic dispersant, p may be a number of 3 or more (for example, 5 to 200). q may be a number of 2 or more (for example, 5 to 200). That is, -(R 2 O) q - may form a polyoxyalkylene chain. The nonionic dispersant may be a polyoxyethylene alkylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly, a polyoxyalkylene chain) in the center. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, a styrene chain, etc., and among them, an oxypropylene chain is preferred.

[0307] 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 (C7-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. Examples of the nonionic dispersant include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene polyoxybutylene alkyl ethers, polyoxyethylene polyoxypropylene glycols, polyethyleneimine ethoxylates, etc.

[0308] 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 kind or a mixture of two or more kinds. The nonionic dispersant may be a mixture of a compound having an HLB (hydrophilic-lipophilic balance) of less than 15 (particularly 5 or less) and a compound having an HLB of 15 or more. Specifically, it is preferably selected from polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene, polyoxypropylene having 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 having an HLB value of less than 7.

[0309] [Cationic Dispersant] The dispersant may contain a cationic dispersant. The cationic dispersant may be a cationic surfactant. The cationic dispersant may be a compound having no amide group.

[0310] The cationic dispersant may be of low molecular weight type (for example, having a molecular weight of 2000 or less, particularly 10000 or less) or of high molecular weight type (for example, having a molecular weight of 2000 or more). The molecular weight of the cationic dispersant may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 1000000 or less, 750000 or less, 500000 or less, 250000 or less, 100000 or less, 50000 or less, 10000 or less, 7500 or less, 5000 or less, 25000 or less, 750 or less, or 250 or less.

[0311] The cationic dispersant may be aliphatic or aromatic, and examples thereof include ammonium salts (e.g., quaternary ammonium salts). The cationic dispersant may also be an oxyethylene-added type ammonium salt. Specifically, amine salt type dispersants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, etc.; quaternary ammonium salt type dispersants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzalkonium chloride, benzethonium chloride, etc.; high molecular weight type cationic dispersants such as polyquaternium-1 to 47, etc. Examples of the cationic dispersant include alkylamine salts, quaternary ammonium salts, etc.

[0312] The low molecular weight type cationic dispersant is R 21 -N + (-R 22 )(-R 23 )(-R 24 )X - [In the formula, R 21 , R 22 , R 23 and R 24 are hydrogen or a hydrocarbon group having 1 to 40 carbon atoms, and X is an anionic group.] It may be a compound represented by. R 21 , R 22 , R 23 and -R 24 Specific examples of are alkyl groups (e.g., methyl group, butyl group, stearyl group, palmityl group), aromatic groups (e.g., benzyl group, phenyl group), etc. Specific examples of X are halogen (e.g., chlorine), acid (e.g., hydrochloric acid, acetic acid). Examples of the cationic dispersant include monoalkyltrimethylammonium salts (alkyl having 4 to 40 carbon atoms), benzalkonium chloride, etc.

[0313] Specifically, the low molecular weight type cationic dispersant has the formula: R 1 p -N +R 2 q X - [wherein, R 1 is a linear and / or branched aliphatic (saturated and / or unsaturated) group having 12 or more carbon atoms (for example, C 12 ~C 50 ), and R 2 is H or an alkyl group having 1 to 4 carbon atoms, a benzyl group, a polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (especially 2, particularly 3) to 50) (CH3 and C2H5 are particularly preferred), and X is a halogen atom (for example, chlorine), or a fatty acid salt having 1 to C4, or a sulfonate having 1 to C4, and p is 1 or 2, q is 2 or 3, and p + q = 4.] It may be an ammonium salt represented by R 1 may have 12 to 50 carbon atoms, for example, 12 to 30 carbon atoms.

[0314] Examples of the low-molecular cationic dispersant may include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydropolyoxyethylene)ammonium chloride, benzyldodecyldi(hydropolyoxyethylene)ammonium chloride, N-[2-(diethylamino)ethyl]oleamide hydrochloride, and the like.

[0315] The polymeric cationic dispersant may be various polymers having cationic groups (e.g., ammonium group, quaternary ammonium group) (e.g., polyquaternium-1 to 47). Examples of the polymeric cationic dispersant include cationized starches, cationized celluloses (e.g., O-(2-hydroxy-3-(trimethylammonio)propyl) hydroxyethyl cellulose chloride), cationized guar gums, cationized xanthan gums, cationized natural products such as chitosan (especially cationized saccharides); polymers of cationic group-containing monomers such as aziridine, vinylimidazole, aminoalkyl methacrylate, N,N,N',N'-tetramethyl-2-butene-1,4-diamine, quaternized dimethylammonium ethyl methacrylate, diallyldimethylammonium chloride, dimethylaminopropylamine, quaternized vinylimidazole, and the like.

[0316] [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.

[0317] 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 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.

[0318] Examples of the anionic dispersant 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. As an example of the anionic dispersant, carboxylate salts (e.g., fatty acid salts) and the like can be mentioned.

[0319] [Amphoteric dispersant] The dispersant may contain an amphoteric dispersant. The amphoteric dispersant may be an amphoteric surfactant.

[0320] 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.

[0321] Examples of the amphoteric dispersant include alanines, imidazolinium betaines, amide betaines, betaine acetate, etc. Specifically, lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylaminoacetic acid betaine, fatty acid amide propyl dimethylaminoacetic acid betaine, etc. can be mentioned.

[0322] [Inorganic dispersant] The dispersant may contain an inorganic dispersant.

[0323] 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.

[0324] Examples of the inorganic dispersant include polyvalent metal phosphates such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, hydroxyapatite; carbonates such as calcium carbonate, magnesium carbonate; silicates such as calcium metasilicate; sulfates such as calcium sulfate, barium sulfate; hydroxides such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, etc.

[0325] [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 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 liquid-repellent compound, and may also be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less.

[0326] 〔Liquid medium〕 The liquid-repellent agent 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 liquid-repellent agent may be a dispersion or a solution. The liquid-repellent agent in the present disclosure may contain at least water.

[0327] Examples of the organic solvent include esters (e.g., esters having 2 to 40 carbon atoms, specifically ethyl acetate, butyl acetate), ketones (e.g., ketones having 2 to 40 carbon atoms, specifically methyl ethyl ketone, diisobutyl ketone), alcohols (e.g., alcohols having 1 to 40 carbon atoms, specifically isopropyl alcohol), aromatic solvents (e.g., toluene and xylene), and petroleum solvents (e.g., alkanes having 5 to 10 carbon atoms, specifically naphtha, kerosene). The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent may contain a compound having at least one 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.

[0328] [Amount of the 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 liquid-repellent compound, 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.

[0329] 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 liquid-repellent compound, 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.

[0330] 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 with respect to 1 part by weight of the liquid-repellent compound, 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.

[0331] 〔Wax〕 The release agent in the present disclosure may contain wax. By containing wax, good liquid repellency can be imparted to the substrate.

[0332] 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, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane). The number of carbon atoms 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.

[0333] 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.

[0334] [Amount of wax] The amount of 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 with respect to 100 parts by weight of the liquid-repellent compound. The amount of wax 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 with respect to 100 parts by weight of the liquid-repellent compound.

[0335] 〔Silicone〕 The repellent agent in the present disclosure may contain silicone (polyorganosiloxane). By containing silicone, in addition to good liquid repellency, it can also have good texture and durability.

[0336] 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.

[0337] 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.

[0338] [Amount of silicone] The amount of silicone 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 with respect to 100 parts by weight of the liquid-repellent compound, and may also be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less with respect to 100 parts by weight of the liquid-repellent compound.

[0339] [Organic acid] The water repellent 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.

[0340] [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 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 with respect to 100 parts by weight of the water repellent compound, and may also be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less. The amount of the organic acid may be adjusted so that the pH of the water repellent is 3 to 10, for example 5 to 9, particularly 6 to 8. The water repellent may be acidic (pH 7 or less, for example 6 or less).

[0341] [Inorganic acid] The water repellent of the present disclosure may contain an inorganic acid. As the inorganic acid, known ones can be used. Examples of the inorganic acid include hydrogen chloride, hydrogen bromide, hydrogen iodide, nitric acid, boric acid, sulfuric acid, and phosphoric acid. In the present disclosure, one kind of inorganic acid may be used, or two or more kinds may be used in combination. By adding an inorganic acid, the stability of the aqueous dispersion can be improved.

[0342] [Amount of inorganic acid] The amount of the inorganic 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 liquid-repellent compound. 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 inorganic acid may be adjusted so that the pH of the liquid-repellent agent is 3 to 10, for example, 5 to 9, particularly 6 to 8. The liquid-repellent agent may be acidic (pH 7 or less, for example, 6 or less).

[0343] 〔Hardening agent〕 The liquid-repellent agent of the present disclosure may contain a hardening agent (active hydrogen-reactive compound or active hydrogen-containing compound).

[0344] The hardening agent (crosslinking agent) in the liquid-repellent agent can harden the liquid-repellent agent well. The hardening agent may be an active hydrogen-reactive compound or an active hydrogen-containing compound that reacts with active hydrogen or an active hydrogen-reactive group. Examples of 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.

[0345] 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.

[0346] 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.

[0347] 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.

[0348] Examples of aromatic aliphatic polyisocyanates are aromatic aliphatic diisocyanates and aromatic aliphatic triisocyanates. Specific examples of aromatic aliphatic 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.

[0349] Examples of aromatic polyisocyanates are aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates are m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate or a mixture thereof, 2,4- or 2,6-tolylene diisocyanate or a mixture thereof, triphenylmethane-4,4',4''-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate, etc. These may be used alone or in combination of two or more.

[0350] 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.

[0351] 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 sizing agent.

[0352] The blocking agent blocks the free isocyanate groups. The blocked polyisocyanate compound can regenerate the isocyanate groups and react easily with hydroxyl groups by heating, for example, to 100 °C or higher, for example, 130 °C or higher. Examples of the blocking agent are phenolic compounds, lactam compounds, aliphatic alcohol compounds, oxime compounds, etc. The polyisocyanate compound can be used alone or in combination of two or more.

[0353] The epoxy compound is a compound having an epoxy group. Examples of the epoxy compound are epoxy compounds having a polyoxyalkylene group, for example, 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.

[0354] 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.

[0355] [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 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more with respect to 100 parts by weight of the liquid repellent compound, and may also be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less.

[0356] [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, anti-slip agents, 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, as other components, other water and / or oil repellents, dispersants, texture 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, ironing property improvers, brightening agents, whitening agents, fabric softening clay, migration inhibitors such as polyvinylpyrrolidone, polymer dispersants, soil release agents, scum dispersants, fluorescent brightening agents 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, enzymes such as cellulase, amylase, protease, lipase, keratinase, etc. as fiber surface modifiers, defoaming agents, silk powder, surface modified products thereof or emulsion dispersions (for example, K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical Co., Ltd.), hydrolyzed silk solution (Kamo), Silkgen G Soluble S (Ichimaru Pharcos)) that can impart silk texture and functions such as moisture absorption and release, anti-pollution agents (for example, nonionic polymer compounds composed of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units (for example, FR627 manufactured by Gohou Chemical Industry Co., Ltd.), SRC-1 manufactured by Clariant Japan, etc.) can be blended. These may be used alone or in combination of two or more.

[0357] [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 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 liquid-repellent compound, and may also be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0358] <Method for producing pulp composition / pulp product> The pulp composition in the present disclosure can be obtained by treating a pulp base material with a liquid-repellent agent containing a liquid-repellent compound.

[0359] The obtained pulp composition can be made into a pulp product by subjecting it to treatment steps such as drying, heating, and shaping, if necessary.

[0360] The liquid-repellent agent in the present disclosure can be applied to the pulp base material by a conventionally known method as a treating agent (particularly a surface treating agent). As the treatment method, the liquid-repellent agent in the present disclosure can be dispersed and diluted in an organic solvent or water, if necessary, and adhered to the inside and / or surface of the pulp base material by a known method such as dipping coating, spray coating, or foam coating, and then dried. The dilution ratio may be appropriately changed depending on the concentration and use of the liquid-repellent agent, but may be 3 to 2000 times, for example, 10 to 100 times. After drying, a pulp product with the solid component of the liquid-repellent agent adhered thereto can be obtained. Also, if necessary, it may be applied together with a suitable cross-linking agent and cured.

[0361] The sizing agent can be applied to the pulp substrate by any of the methods known for treating the pulp substrate with a liquid. The pulp substrate may be immersed in the sizing agent, or the pulp substrate and the sizing agent may be mixed, or a solution may be adhered or sprayed onto the pulp substrate. The treated pulp substrate is preferably dried and cured by heating in order to exhibit liquid repellency. The heating temperature may be, for example, 100°C to 200°C, 100°C to 170°C or 100°C to 120°C. In the present disclosure, the heating time may be 5 seconds to 60 minutes, for example 30 seconds to 3 minutes.

[0362] As a method for treating a pulp base material, an internal addition treatment method of adding a sizing agent to the pulp base material before papermaking (for example, in the form of a pulp slurry), or an external addition treatment method of applying a sizing agent to the pulp base material after papermaking (for example, a pulp product) can be used. Examples of the internal addition treatment method include mixing, dipping, etc., and may include a step of adding a sizing agent to the pulp slurry and stirring and mixing. Examples of the external addition treatment method include spraying, coating, dipping treatment, foam coating, etc., and specifically include a pond type two-roll size press, a gate roll type, and a rod metering size press, etc. The treatment may be an external addition treatment or an internal addition treatment. For example, when the pulp base material is paper, it may be coated on the paper, or a solution may be adhered or sprayed on the paper, or it may be mixed and treated with the pulp slurry before papermaking. When the pulp base material is a fiber material, examples of the treatment method include padding treatment, dipping treatment, spraying treatment, and coating treatment. Examples of the padding treatment include a method using a padding device described on pages 396-397 of the Fiber Dyeing Processing Dictionary (published in 1963 by Nikkansen Shimbunsha) and pages 256-260 of Color Dyeing Chemistry III (published in 1975 by Jitskyo Publishing Co., Ltd.). Examples of the coating treatment include a method using a coating machine described on pages 473-477 of the General List of Dyeing Finishing Equipment (published in 1981 by Sen’i Sha). Examples of the dipping treatment include a method using a batch dyeing machine described on pages 196-247 of the General List of Dyeing 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 sprays it, and a method using an air spray of a hydraulic atomization method.

[0363] The treatment method may be an internal addition treatment in which a sizing agent is added to the pulp slurry before papermaking. The internal addition treatment may include one or more of the steps of adding a sizing agent to the pulp slurry and stirring and mixing it, suction dewatering 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 molded product, and forming and drying the intermediate pulp molded product with a heated mold to obtain a pulp molded product, but 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, may be 300 °C or lower, 250 °C or lower, or 200 °C or lower, and particularly may be 80 °C to 180 °C. By performing the heat treatment within such a temperature range, excellent oil resistance and water resistance can be exhibited. An external addition treatment may be performed on the internally added pulp base material, treated with a sizing agent, and a further liquid-repellent compound may be adhered to the surface.

[0364] The treatment method may be an external addition treatment in which a sizing agent is applied to the pulp base material after papermaking. The size press of the external addition treatment can also be classified as follows by the coating method. One coating method is a so-called pond-type two-roll size press in which a coating liquid (size 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 size 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 size liquid is applied by a surface transfer type, and a rod metering size press. In the pond-type two-roll size press, the size liquid easily penetrates into the paper, and in the surface transfer type, the size 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 a larger coating layer 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 may be optionally accompanied by a heat treatment in a temperature range up to 300 °C, for example up to 200 °C, particularly 80 °C to 180 °C, depending on the properties of the paper after simple drying at room temperature or high temperature, and can exhibit excellent oil resistance and water resistance.

[0365] Specific examples of pulp products include paper, paper containers, pulp molded products, food packaging materials, food containers, base paper for gypsum board, base paper for coating, medium-weight 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 base paper for coating, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper, and neutral information paper, etc. Examples of preferred pulp products include food packaging materials and food containers, and particularly pulp molded products for food contact applications.

[0366] As described above, although the embodiments have been explained, it will be understood that various changes in form and details are possible without departing from the spirit and scope of the claims.

Examples

[0367] Hereinafter, the present disclosure will be described in detail with reference to examples, but the present disclosure is not limited to these examples.

[0368] <Test method> The test procedure is as follows.

[0369] [Volume fraction and median diameter (D50) of particles] For the liquid-repellent compound and the aqueous dispersion, the volume fraction of particles of 100 μm or more, the volume fraction of particles of 10 μm or more, and the median diameter (D50) were calculated from the volume-based frequency distribution (volume distribution) obtained by measurement with a laser diffraction / scattering device.

[0370] [Preparation Example 1: Preparation of decaglycerol dodecabenzenesulfonate dispersion] As a polyol-modified product, 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. 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 19.8 μm.

[0371] [Preparation Example 2: Preparation of Ethylene Bisstearic Acid Amide Dispersion] 2 g of N,N'-ethylene bisstearic acid amide (bio-based degree: 97%, melting point: 143°C, pulverized particle size: 18 μm) subjected to pulverization treatment with a jet mill, 0.2 g of polyethylene glycol trimethylnonyl ether (HLB 13), and 17.8 g of water were mixed to obtain a water-dispersion composition (volume occupancy ratio of particles of 100 μm or more: 3.9%, volume median diameter: 18 μm).

[0372] [Preparation Example 3: Preparation of Ethylene Bishydroxystearic Acid Amide Dispersion] 2 g of N,N'-ethylene-bis-12-hydroxystearylamide (bio-based degree: 95%, melting point: 145°C, pulverized particle size: 17 μm) subjected to pulverization treatment with a jet mill, 0.2 g of EO / PO polyalkylene glycol natural alcohol ether, and 17.8 g of water were mixed to obtain a water-dispersion composition (volume occupancy ratio of particles of 100 μm or more: 5%, volume median diameter: 17 μm).

[0373] [Preparation Example 4: Preparation of Ethylene Bisoleic Acid Amide Dispersion] 2 g of N,N’-ethylenebisoleic acid amide (bio-based degree: 96%, melting point: 116 °C, pulverized particle size: 24 μm) subjected to pulverization treatment by a jet mill, 0.2 g of an EO / PO polyalkylene glycol alcohol ether (HLB 7), and 17.8 g of water were mixed to obtain an aqueous dispersion composition. (Volume occupancy ratio of particles of 100 μm or more: 0%, volume median diameter: 24 μm)

[0374] [Preparation Example 5: Preparation of xylylenebis(hydroxystearic acid amide) dispersion] 2 g of N,N-xylylene-bis-12-hydroxystearylamide (bio-based degree: 83%, pulverized particle size: 9 μm) subjected to pulverization treatment by a jet mill, 0.2 g of a polyethylene glycol trimethylnonyl ether (HLB 13), and 17.8 g of water were mixed to obtain an aqueous dispersion composition (volume occupancy ratio of particles of 100 μm or more: 0%, volume median diameter: 9 μm).

[0375] [Preparation Example 6: Preparation of hexamethylenebis(hydroxystearic acid amide) dispersion] 2 g of N,N’-hexamethylene-bis-12-hydroxystearylamide (bio-based degree: 85%, melting point: 134 °C, pulverized particle size: 12 μm) subjected to pulverization treatment by a jet mill, 0.2 g of an EO / PO polyalkylene glycol natural alcohol ether, and 17.8 g of water were mixed to obtain an aqueous dispersion composition. (Volume occupancy ratio of particles of 100 μm or more: 3.5%, volume median diameter: 12 μm)

[0376] [Production of pulp mold] Using an automatic mold forming machine, a pulp mold was formed. A net-like body was placed on top of a metal pulp mold forming die provided with a large number of suction holes at the bottom. A metal tank was placed at the top, and a mixture of pulp slurry and a water-dispersible release agent (pulp composition) was put into the upper metal tank. From the side opposite to the side where the net-like body of the pulp mold forming die was placed, the pulp composition was sucked and dehydrated through the pulp mold forming die and the net-like body by a vacuum pump, and the solid content (such as pulp) contained in the pulp composition was deposited on the net-like body to obtain a pulp mold intermediate. Next, the obtained pulp mold intermediate was dried under a pressure of 0.05 to 5 MPa from above and below with a metal osmium mold heated to 60 to 250 °C. Thereby, a pulp mold product formed into the shape of a container was manufactured.

[0377] [Oil resistance test] 100 mL of corn oil at 65 °C was poured into the pulp mold, and after leaving it at room temperature for 45 minutes, the corn oil was taken out from the pulp mold, and the degree of stain of the pulp mold was evaluated. Depending on the degree of penetration, evaluation values were set as follows. 5: No stain on the inside. 4: There is stain on the inside. No stain on the back side. 3: There is stain on the inside. There is a slight stain on the back side. 2: There is stain on the inside. The stain on the back side is less than 50% of the area. 1: There is stain on the inside. The stain on the back side is 50% or more and less than 100% of the area. 0: The stain has leaked out to the entire back side.

[0378] <Example 1> An aqueous pulp slurry with a concentration of 0.5 wt% containing 25% bagasse pulp and 75% wood pulp with respect to the total amount of pulp was prepared. The decaglycerol deca behenyl ester dispersion of Preparation Example 1 was added so as to be in a ratio of 3 wt% with respect to 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 oil resistance test of the produced pulp mold was carried out, the oil resistance performance was 4 points. The results are shown in Table 1.

[0379] <Example 2> An aqueous pulp slurry with a concentration of 0.5 wt% containing 100% bagasse pulp based on the total pulp amount was prepared. The decaglycerol dodecabenyl ester dispersion of Preparation Example 1 was added so as to be in a ratio of 3 wt% with respect to the pulp on a solid content 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 oil resistance test of the produced pulp mold was carried out, the oil resistance performance was 4 points. The results are shown in Table 1.

[0380] <Example 3> When preparing the pulp composition, a pulp mold was produced in the same manner as in Example 1 except that 0.45 wt% of AKD (alkyl ketene dimer) was added to the pulp. When the oil resistance test of the produced pulp mold was carried out, the oil resistance performance was 4 points. The results are shown in Table 1.

[0381] <Example 4> When preparing the pulp composition, a pulp mold was produced in the same manner as in Example 1 except that 0.1 wt% of a rosin sizing agent was added to the pulp. When the oil resistance test of the produced pulp mold was carried out, the oil resistance performance was 4 points. The results are shown in Table 1.

[0382] <Example 5> An aqueous pulp slurry was prepared in the same manner as in Example 1. The ethylene bisstearamide dispersion of Preparation Example 2 was added so as to be in a ratio of 2 wt% with respect to the pulp on a solid content basis, and a pulp composition was prepared. Similarly, a pulp mold was produced and the oil resistance test was carried out. As a result, the oil resistance performance was 4 points. The results are shown in Table 1.

[0383] <Example 6> In the same manner as in Example 1, an aqueous pulp slurry was prepared. The ethylene bis(hydroxystearic acid amide) dispersion of Preparation Example 3 was added so as to have a ratio of 3 wt% with respect to the pulp on a solid content basis, and a pulp composition was prepared. The pulp composition was put into an automatic mold forming machine to produce a pulp mold. When a pulp mold was produced in the same manner and an oil resistance test was carried out, the oil resistance performance was 4 points. The results are shown in Table 1.

[0384] <Example 7> In the same manner as in Example 1, an aqueous pulp slurry was prepared. The ethylene bis(oleic acid amide) dispersion of Preparation Example 4 was added so as to have a ratio of 7 wt% with respect to the pulp on a solid content basis, and a pulp composition was prepared. In the same manner, a pulp mold was produced, and when an oil resistance test was carried out, the oil resistance performance was 4 points. The results are shown in Table 1.

[0385] <Example 8> In the same manner as in Example 1, an aqueous pulp slurry was prepared. The xylylene bis(hydroxystearic acid amide) dispersion of Preparation Example 5 was added so as to have a ratio of 2 wt% with respect to the pulp on a solid content basis, and a pulp composition was prepared. In the same manner, a pulp mold was produced, and when an oil resistance test was carried out, the oil resistance performance was 4 points. The results are shown in Table 1.

[0386] <Example 9> In the same manner as in Example 1, an aqueous pulp slurry was prepared. The hexamethylene bis(hydroxystearic acid amide) dispersion of Preparation Example 6 was added so as to have a ratio of 3 wt% with respect to the pulp on a solid content basis, and a pulp composition was prepared. In the same manner, a pulp mold was produced, and when an oil resistance test was carried out, the oil resistance performance was 4 points. The results are shown in Table 1.

[0387] <Comparative Example 1> An aqueous pulp slurry having a concentration of 0.5 wt% containing 100% wood pulp with respect to the total amount of pulp was prepared, and a pulp mold was produced in the same manner as in Example 1. When an oil resistance test of the produced pulp mold was carried out, the oil resistance performance was 3 points. The results are shown in Table 1.

[0388] <Comparative Example 2> An aqueous pulp slurry with a concentration of 0.5 wt% containing 100% wood pulp with respect to the total pulp amount was prepared, and a pulp mold was produced in the same manner as in Example 7. When the oil resistance test of the produced pulp mold was carried out, the oil resistance performance was 3 points. The results are shown in Table 1.

[0389] <Comparative Example 3> An aqueous pulp slurry with a concentration of 0.5 wt% containing 100% bagasse pulp with respect to the total pulp amount was prepared. Sucrose fatty acid ester dispersion (SEFOSE 1618U (manufactured by Procter & Gamble Chemicals)) was added so as to be in a ratio of 3 wt% with respect to the pulp in terms of solid content, and further 0.1 wt% of a polyamine resin was added as a combined chemical to the pulp to prepare a pulp composition. The pulp slurry was put into an automatic mold forming machine to produce a pulp mold. When the oil resistance test was carried out, the oil resistance performance was 1 point. The results are shown in Table 1.

[0390] <Comparative Example 4> An aqueous pulp slurry with a concentration of 0.5 wt% containing 25% bagasse pulp and 75% wood pulp with respect to the total pulp amount was prepared, and a pulp composition was prepared in the same manner as in Comparative Example 3. A pulp mold was produced and the oil resistance test was carried out. As a result, the oil resistance performance was 2 points. The results are shown in Table 1.

[0391] <Comparative Example 5> An aqueous pulp slurry with a concentration of 0.5 wt% containing 25% bagasse pulp and 75% wood pulp with respect to the total pulp amount was prepared. The pulp slurry was put into an automatic mold forming machine to produce a pulp mold. When the oil resistance test and water resistance test of the produced pulp mold were carried out, both the oil resistance test and the water resistance test were 0 points.

[0392] <Comparative Example 6> An aqueous pulp slurry with a concentration of 0.5 wt% containing 100% bagasse pulp with respect to the total pulp amount was prepared. The pulp slurry was put into an automatic mold forming machine to produce a pulp mold. When the oil resistance test and water resistance test of the produced pulp mold were carried out, the results were both 0 points in the oil resistance test and water resistance test.

[0393] The results are summarized in the following table. [Table 1] TIFF0007712568000008.tif141164

Claims

1. A pulp composition comprising a liquid-repellent compound and a pulp base material, wherein the liquid-repellent compound is a compound having a monovalent hydrocarbon group with 6 to 40 carbon atoms which may have a substituent, and is not a fatty acid ester having a glycoside bond, and the pulp base material contains bagasse pulp, the pulp composition.

2. The liquid-repellent compound is, -OC(=O)R, -COOR, -NHCOR, and -CONHR wherein R is each independently a monovalent hydrocarbon group with 6 to 40 carbon atoms which may have a substituent.], The pulp composition according to claim 1, having at least one group selected from the group consisting of.

3. The liquid-repellent compound is a compound obtained by modifying an amine, a polyol, or a polycarboxylic acid with a hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, the pulp composition according to claim 1.

4. The amount of the liquid-repellent compound is 0.5% by weight or more and 25% by weight or less based on the pulp base material, the pulp composition according to claim 1.

5. In the pulp base material, the amount of the bagasse pulp is 20% by weight or more and 100% by weight or less, the pulp composition according to claim 1.

6. The pulp composition according to claim 1, further comprising a dispersant.

7. The pulp composition according to claim 1, further comprising a paper additive.

8. The pulp composition according to claim 1, further comprising a sizing agent.

9. The pulp composition according to claim 1, further comprising a sulfate band.

10. A pulp molded article formed from the pulp composition according to any one of claims 1 to 9.

11. The pulp molded article according to claim 10, which is for food contact use.

12. A method for producing a pulp composition, comprising a step of treating a pulp base material with a liquid-repellent agent containing a liquid-repellent compound, wherein the liquid-repellent compound is a compound having a monovalent hydrocarbon group with 6 to 40 carbon atoms which may have a substituent, and is not a fatty acid ester having a glycoside bond, and the pulp base material contains bagasse pulp, the method for producing a pulp composition.

13. The liquid-repellent compound is, -OC(=O)R, -COOR, -NHCOR, and -CONHR wherein R is each independently a monovalent hydrocarbon group with 6 to 40 carbon atoms which may have a substituent.], The method for producing the pulp composition according to claim 12, having at least one group selected from the group consisting of

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