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, and in particular to pulp compositions having oil and / or water resistance. [Background technology]

[0002] Patent Document 1 discloses that a composition containing a sugar fatty acid ester and hemicellulose or lignin can be used to improve the barrier function of cellulosic materials.

[0003] In the composition described in Patent Document 1, sugar fatty acid ester is an essential component, and the use of other components in place of sugar fatty acid ester is not examined. In addition, there is no disclosure that the composition exhibits excellent oil resistance or water resistance. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] WO2021 / 019468 Summary of the Invention [Problem to be solved by the invention]

[0005] The present disclosure aims to provide novel pulp compositions that are resistant to oil and / or water. [Means for solving the problem]

[0006] The present disclosure includes the following aspects: [Section 1] A pulp composition comprising a liquid repellent compound and a pulp substrate, 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 glycosidic bond, The pulp composition, wherein the pulp base material comprises bagasse pulp. [Section 2] The liquid repellent compound is -OC(=O)R, -COOR, -NHCOR, and -CONHR [In the formula, each R is independently a monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent.] Item 2. The pulp composition according to item 1, having at least one group selected from the group consisting of: [Section 3] 3. The pulp composition according to item 1 or 2, wherein the liquid repellent compound is an amine, a polyol, or a polycarboxylic acid modified with a hydrocarbon group having 6 to 40 carbon atoms and which may have a substituent. [Section 4] 4. The pulp composition according to any one of items 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. [Section 5] 5. The pulp composition according to any one of items 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. [Section 6] Item 6. The pulp composition according to any one of items 1 to 5, wherein the pulp composition contains a dispersant. [Section 7] Item 7. The pulp composition according to any one of items 1 to 6, wherein the pulp composition comprises a combination chemical for paper. [Section 8] Item 8. The pulp composition according to any one of items 1 to 7, wherein the pulp composition contains a sizing agent. [Section 9] Item 9. The pulp composition according to any one of items 1 to 8, wherein the pulp composition contains aluminum sulfate. [Section 10] Item 10. A molded pulp product molded from the pulp composition according to any one of items 1 to 9. [Section 11] Item 11. The pulp molded product according to item 10, which is for food contact applications. [Section 12] A method for producing a pulp composition, comprising treating a pulp substrate with a repellent comprising a liquid repellent compound, 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 glycosidic bond, The method for producing a pulp composition, wherein the pulp base material comprises bagasse pulp. [Section 13] The liquid repellent compound is -OC(=O)R, -COOR, -NHCOR, and -CONHR [In the formula, each R is independently a monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent.] Item 13. The method for producing a pulp composition according to item 12, wherein the pulp composition has at least one group selected from the group consisting of: Effect of the Invention

[0007] The pulp composition of the present disclosure may have excellent oil and / or water resistance. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] <Terminology> As used herein, the term "n-valent group" refers to a group having n bonds, i.e., a group that forms n bonds. The term "n-valent organic group" refers to an n-valent group containing carbon. Such an organic group is not particularly limited, but may be a hydrocarbon group or a derivative thereof. The derivative of a hydrocarbon group refers to a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, halogen, etc. at the end or molecular chain of the hydrocarbon group.

[0009] As used herein, the term "hydrocarbon group" refers to a group containing carbon and hydrogen, which is a group obtained by removing a hydrogen atom from a hydrocarbon. Such a hydrocarbon group includes, but is not limited to, C 1-20Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. The hydrocarbon group may contain one or more ring structures. The hydrocarbon group may be substituted with one or more substituents.

[0010] In this specification, when a term (symbol) that may occur multiple times in a chemical structure is defined, the definition applies independently at each occurrence, unless otherwise stated, regardless of whether "independently at each occurrence," "independently of each other," "independently of each other," or similar expressions are explicitly stated.

[0011] It should be understood that the chemical structures illustrated herein do not encompass chemical structures that would be recognized by those of ordinary skill in the art as being chemically impossible or extremely unstable.

[0012] <Pulp composition> The pulp composition of the present disclosure includes a liquid repellent compound and a pulp base material. The pulp composition of the present disclosure may have excellent oil 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 repellent agent containing a liquid repellent compound, and the amount of the repellent agent added or the composition of the repellent agent may be adjusted so that each component is present in a desired amount. Each component that may be contained in the repellent agent may be added to the pulp composition as a separate additive.

[0014] The pulp composition of the present disclosure may not contain any of the compounds selected from the group consisting of compounds having a fluoroalkyl group with 8 or more carbon atoms, compounds having a perfluoroalkyl group with 8 or more carbon atoms, compounds having a fluoroalkyl group with 4 or more carbon atoms, compounds having a perfluoroalkyl group with 4 or more carbon atoms, compounds having a perfluoroalkyl group, compounds having a fluoroalkyl group, and compounds having a fluorine atom. The pulp composition of the present disclosure can impart liquid repellency to a substrate even if it does not contain 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 amount of each component may be adjusted to achieve such a pH.

[0016] [Pulp base material] The pulp composition includes a pulp base material. The pulp base material is composed of pulp, which may be wood pulp, non-wood pulp, recycled paper pulp, etc., and includes at least bagasse pulp.

[0017] [Wood pulp] Wood pulp includes coniferous kraft pulp obtained from the fir and pine genus, and hardwood kraft pulp obtained from the Acacia, Eucalyptus, Beech, and Populus genus (e.g., poplar). Examples of coniferous kraft pulp include unbleached coniferous kraft pulp (NUKP), bleached coniferous pulp (NBKP), semi-bleached coniferous kraft pulp (NSBKP), and softwood 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 hardwood sulfite pulp. The pulps used may be used alone or in combination. In addition to kraft pulp, there are softwood kraft pulp and hardwood kraft pulp, as well as mechanical pulp such as stone ground pulp (SGP), pressurized stone ground pulp (PGW), refiner ground pulp (RGP), thermo ground pulp (TGP), chemi-ground pulp (CGP), groundwood pulp (GP), thermomechanical pulp (TMP), etc. Furthermore, waste paper pulp includes disintegrated waste paper pulp, disintegrated and deinked waste paper pulp, or disintegrated, deinked and bleached waste paper pulp, which are produced from brown waste paper, waste kraft envelope paper, magazine paper, newspaper paper, flyer paper, office paper, cardboard paper, white waste paper, Kent waste paper, imitation waste paper, and land certificate waste paper.

[0018] [Non-wood pulp] Examples of non-wood pulp include pulp obtained from bagasse, kenaf, bamboo, linter, cotton, linen, hemp, ramie, straw, esparto, Manila hemp, sisal, jute, flax, mulberry, mitsumata, paper mulberry, and the like.

[0019] [Pulp fiber length] From the viewpoint 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, and even more preferably 0.5 mm or more, and from the viewpoint of ease of production, it is preferably 5.0 mm or less, more preferably 4.0 mm or less, even more preferably 3.0 mm or less, particularly preferably 2.0 mm or less, and most preferably 1.2 mm or less.

[0020] [Pulp fiber width] From the viewpoint of improving oil resistance, the average fiber diameter of the pulp is preferably 5 μm or more, Preferably, the thickness is 10 μm or more, more preferably, 15 μm or more, and more preferably, 5 0 μm or less, more preferably 40 μm or less, and further 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 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 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 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 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] [Pulp base material form] 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., and specific examples include pulps such as bleached or unbleached chemical pulps such as kraft pulp and sulfite pulp, bleached or unbleached high-yield pulps such as groundwood pulp, mechanical pulp and thermomechanical pulp; pulp slurries containing the above pulps; and pulp products such as paper, paper containers, and pulp molded products.

[0025] [Amount of pulp base material] The amount of the pulp base material in the pulp composition 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, and may 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 in the pulp composition is 30% by weight or less, and when the pulp composition is prepared by external addition, the amount of the pulp base material in the pulp composition may be 75% by weight or more.

[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 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 comprise a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent, typically an aqueous medium, especially water. The liquid medium may comprise a liquid medium derived from a repellent agent.

[0028] [Amount of liquid medium] The amount of the liquid medium in the pulp composition 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, and may 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 in the pulp composition is 50% by weight or more, particularly 90% by weight or more, and when the pulp composition is prepared by external addition, the amount of the liquid medium in the pulp composition is 30% by weight or less, particularly 10% by weight or less.

[0029] [Liquid repellent compound] The pulp composition contains a liquid repellent compound. For details of the types of liquid repellent compounds, the explanation of the liquid repellent compounds in <Repellent Agent> is incorporated herein 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, preferably 0.5% by weight or more, and may 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 amine-modified liquid repellent compound, relative to the pulp base material, 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, preferably 0.5 wt% or more, and may be 25 wt% or less, 20 wt% or less, 15 wt% or less, 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, for example, 15 wt% or less, 5.0 wt% or less, or 3.0 wt% or less.

[0032] The amount of the polyol-modified liquid repellent compound relative to the pulp base material 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, preferably 0.5 wt% or more, and may be 25 wt% or less, 20 wt% or less, 15 wt% or less, 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, for example, 15 wt% or less, 5.0 wt% or less, or 3.0 wt% or less.

[0033] The amount of the liquid repellent compound which is a polycarboxylic acid modified product, relative to the pulp base material, 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, preferably 0.5 wt% or more, and may be 25 wt% or less, 20 wt% or less, 15 wt% or less, 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, for example, 15 wt% or less, 5.0 wt% or less, or 3.0 wt% or less.

[0034] The liquid repellent compound may be added to the surface of a pulp substrate (e.g., a pulp product such as paper, a paper container, or a pulp molded product) for external addition treatment. The amount of the liquid repellent compound contained in the coating layer formed by external addition treatment is 0.01 g / m 2 More than 0.03g / m 2 More than 0.05g / m 2 More than 0.1g / m 2 More than 0.3g / m 2 More than 0.5g / m 2 or more, or 1.0 g / m 2 or more, and 5.0 g / m 2 Below 4.0g / m 2 Below 3.0g / m 2 Below 2.0g / m 2 Below 1.0g / m 2 Below 0.5g / m 2 Below 0.3g / m 2 or less than 0.1 g / m 2 It may be the following:

[0035] [Dispersant] The pulp composition may contain a dispersant. For details of the types of dispersants, the explanation of dispersants in <Repellent Agent> is incorporated herein by reference.

[0036] [Amount of dispersant] The amount of the dispersant 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, and may 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, and more preferably 3.0% by weight or less.

[0037] [Paper strength agent] The pulp composition may include a strength agent. Examples of strength agents include: Polyacrylamide-based paper strength agents such as cationic polyacrylamide, anionic polyacrylamide, and amphoteric polyacrylamide; polysaccharide-based paper strength agents such as starch, enzyme-modified starch, thermochemically modified starch, oxidized starch, esterified starch, etherified starch (e.g., hydroxyethylated starch, etc.), aldehyde 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, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, chitin nanofiber, cellulose nanofiber, and pullulan, and modified polysaccharides thereof (e.g., modified polysaccharides having hydroxyl groups or cationic groups introduced therein); Polyamide-based paper strength agents such as polyamide resins, polyamine resins, polyamide-polyamine resins, polyamide-epichlorohydrin resins, polyamide-polyamine-epichlorohydrin resins, polyamide-polyurea-formaldehyde resins, and epoxidized polyamide resins; Urea / melamine-based paper strength agents such as urea resin, melamine resin, urea-formaldehyde resin, and melamine-formaldehyde resin; polyvinyl alcohol-based paper strength 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, and terminal alkyl-modified polyvinyl alcohol; These include styrene-butadiene copolymers, polyvinyl acetate, vinyl chloride-vinyl acetate copolymers, polyvinyl chloride, polyvinylidene chloride, polyacrylic esters, fatty acid diamides, polyethyleneimine resins, and ketone aldehyde resins. In the present disclosure, the paper strength agent is preferably a polyacrylamide-based paper strength agent, a polysaccharide-based paper strength agent, or a polyamide-based paper strength agent.

[0038] [Amount of paper strength agent] The amount of the strength 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, and may 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, and is 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-based sizing agents (e.g., acidic rosin-based sizing agents, neutral rosin-based sizing agents), alkyl ketene dimers, and alkenyl succinic anhydrides.

[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, and may 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, based on the pulp.

[0041] [Other additives] In addition to the above, the pulp composition may contain other additives such as paper-related chemicals used in the manufacture of pulp products, such as fixing agents (e.g., aluminum sulfate), coagulants / flocculants (e.g., polyamine resins), retention aids (e.g., polyacrylamide resins), organic acids (e.g., formic acid, acetic acid), dyes, slime control agents, and defoamers.

[0042] [Amount of other additives] The amount of the other additives may be 0.01% by weight or more, 0.1% by weight or more, 1% by weight or more, 3% by weight or more, or 5% by weight or more, and may 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, based on the pulp base material.

[0043] <Repellent> The repellent agent in the present disclosure can be adhered to a substrate (particularly a pulp substrate) to impart liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or stain resistance, to the substrate, and can also function as a water resistance agent, oil resistance agent, water repellent agent, oil repellent agent, and / or stain resistance agent.

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

[0045] The repellent agent in the present disclosure may not contain any compound selected from the group consisting of a compound having a fluoroalkyl group having 8 or more carbon atoms, a compound having a perfluoroalkyl group having 8 or more carbon atoms, a compound having a fluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group, a compound having a fluoroalkyl group, and a compound having a fluorine atom. The repellent agent in the present disclosure can impart liquid repellency to a substrate even if it does not contain these fluorine compounds.

[0046] The volumetric ratio of particles of 100 μm or more in the repellent of the present disclosure measured by a laser diffraction scattering method may be 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 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 for setting the volumetric ratio of particles of 1 μm or more measured by a laser diffraction scattering method to the above range is not limited, but for example, the particles in the raw material and / or dispersion may be finely divided using a grinder, homogenizer, or the like.

[0047] The volume median diameter of the repellent agent of the present disclosure, as measured by a laser diffraction scattering method, is 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. Alternatively, it may be 100 μm or less, 90 μm or less, 80 μm or less, 70 μm or less, 60 μm or less, 50 μm or less, 40 μm or less, 30 μm or less, 20 μm or less, 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, and is preferably 1 μm or less. In the present disclosure, the volume median size refers to the median size (D50) in the volume-based particle size distribution by the laser diffraction scattering method.

[0048] The average particle size 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 repellent (e.g., oil-resistant agent for pulp) which is the water-dispersed 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 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 size in the above range, for example, a grinder, a homogenizer, or the like may be used to finely pulverize the particles in the raw material and / or the dispersion. Incidentally, 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. It may be q / g or more, -200μeq / g or more, -50μeq / g or more, and may be 5000μeq / g or less, 2500μeq / g or less, 1000μeq / g or less, 750μeq / g or less, 500μeq / g or less, 400μeq / g or less, 350μeq / g or less, 300μeq / g or less, 200μeq / g or less, 100μeq / g or less, or 50μeq / g or less, preferably 1000μeq / g or less, more preferably 500μeq / g or less, for example 300μeq / g or less. In particular, the ionic charge density in the repellent of the present disclosure is preferably -600μeq / g or more and 100μeq / g or less. The ionic charge density in the repellent of the present disclosure can be measured, for example, by the following method.

[0050] A sample liquid with a solid content of 0.1 g / L is used to measure the anion demand with a particle charge meter (BTG MUTEK PCD-06) using a 1 / 1000 N potassium polyvinyl sulfonate solution, and the ionic charge density (cationic charge density) is calculated from the following formula (1). Alternatively, the cation demand is measured in the same manner using a polydiallyldimethylammonium chloride solution instead of potassium polyvinyl sulfonate, and the ionic charge density (anionic charge density) is calculated from the following formula (1). Ionic charge density (μeq / g) = A / B (1) A: Cation demand or anion demand (μeq / L) B: Sample liquid concentration (g / L)

[0051] [Liquid repellent compound] The liquid repellent compounds of the present disclosure are capable of adhering to a substrate (particularly a pulp substrate) to impart liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or stain resistance, to the substrate.

[0052] [Characteristics, 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 be 100° or less, 90° or less, or 75° or less. When the liquid repellent compound has an HD contact angle equal to or greater than the above lower limit, the liquid repellency (particularly oil repellency) can be imparted to the substrate satisfactorily. The HD contact angle is the static contact angle of the liquid repellent compound with respect to the spin-coated film, and is obtained by dropping 2 μL of HD onto the spin-coated film and measuring the contact angle 1 second after the drop lands.

[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 be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. When the liquid repellent compound has a water contact angle equal to or greater than the above lower limit, it can impart good liquid repellency (particularly water repellency) to the substrate. The water contact angle is the static contact angle of the liquid repellent compound with respect to the spin-coated film, and is obtained by dropping 2 μL of water on the spin-coated film and measuring the contact angle 1 second after the drop has landed.

[0055] The liquid repellent compound is preferably a biobased compound having carbon of biobased origin. The biobased degree is measured in accordance with ASTM D6866. The biobased degree may be 20% or more, preferably 30% or more, more preferably 50% or more, even more preferably 60% or more, even more preferably 70% or more, and most preferably 80% or more or 90% or more, for example, 100%. A high biobased degree means that a small amount of fossil resource-based materials, such as petroleum, is used, and from this perspective, the higher the biobased degree of the liquid repellent compound, the more preferable it is.

[0056] The biodegradability of the liquid repellent compound after 180 days is preferably 5% or more. Since the environmental load is reduced, the higher the biodegradability, the more preferable. The biodegradability of the liquid repellent compound after 180 days may be, for example, 10% or more, 20% or more, 30% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, preferably 30% or more, more preferably 50% or more, even more preferably 70% or more, and most preferably 80% or more. The biodegradability of the liquid repellent compound after 60 days is preferably 5% or more. Since the environmental load is reduced, the higher the biodegradability, the more preferable. The biodegradability of the liquid repellent compound after 60 days may be, for example, 10% or more, 15% or more, 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, or 45% or more, preferably 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, and is preferably 40°C or more, and may 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 group selected from the group consisting of a fluoroalkyl group having 8 or more carbon atoms, a perfluoroalkyl group having 8 or more carbon atoms, a fluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group, a fluoroalkyl group, and a fluorine atom. Even if the 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] (Optionally substituted monovalent hydrocarbon group) 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 is preferably an aliphatic hydrocarbon group. The hydrocarbon group may be branched, cyclic, or linear, and is more preferably linear.

[0062] The number of carbon atoms in the hydrocarbon group may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 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 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 halogen atoms (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms at each occurrence). The substituent may or may not have active hydrogen. The number of the substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the hydrocarbon group having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less. For example, the hydrocarbon group may have 1 to 3 (eg, 1) -OR' (particularly -OH) as a substituent (eg, other than at a terminal position).

[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 hydroxyl group of a compound having a structure having a glycosidic bond (typically a sugar (monosaccharide or polysaccharide)) via an ester bond. The use of such a fatty acid ester is not preferred because it may reduce liquid repellency.

[0065] [Examples of liquid repellent compounds] An example of the liquid repellent compound is a compound having a hydrocarbon group having a carbon number of 6 to 40. Examples of the hydrocarbon group and the preferred range are as described above.

[0066] The liquid repellent compounds are -O(C=O)R, -COOR, -NHCOR, and -CONHR. [In the formula, each R is independently a monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent.] The compound 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 sulfoneurea group, a sulfoneurethane group, or a sulfonimide group (e.g., 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-, -OC(=O)-, -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'-, or -SONR'- (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) in each occurrence). The liquid repellent compound may be a compound in which a raw material compound and a modifying group (particularly the monovalent hydrocarbon group which may have the above-mentioned substituent) are bonded via at least one of these groups. The liquid-repellent compound may include an amide structure. The liquid-repellent compound may have at least an amide structure, thereby improving the liquid repellency. Here, the amide structure may be an amide structure in a broad sense, and may be selected from an amide structure 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 sulfone urethane group, a sulfone urea group, a sulfone imide group, and the like. 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 (each group may be inverted). Here, at least one of the bonds possessed by N in 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 to 40 carbon atoms, which may have a substituent. These are also referred to as amine-modified compounds, polyol-modified compounds, and polycarboxylic acid-modified compounds, respectively, in this specification, and will be described in detail separately.

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

[0070] [Amine Modified Compounds] As an example of the liquid repellent compound, an amine-modified compound will be described below. The amine-modified compound is an amine compound that has been chemically modified to exhibit liquid repellency.

[0071] Due to its structure, the amine-modified compound in the present disclosure has excellent dispersibility in liquid media, and the repellent of the present disclosure can have stable performance. Repellents that use polymer-type compounds as active ingredients tend to have a wide molecular weight distribution and contain relatively large amounts of impurity components. On the other hand, the amine-modified compound can be made into a low molecular weight compound, and the molecular weight distribution can be narrowed (unitized), which can result in good performance.

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

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

[0074] The amine-modified product in the present disclosure may be a polyamide having a plurality of amide structures, for example, a polyamide having a plurality of modifying groups (for example, Z N ) may be a polyamide modified via an amide structure. 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 (a starting amine compound) with a monovalent hydrocarbon group having 6 to 40 carbon atoms, which 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 which may have a substituent. From the viewpoint of improving liquid repellency, the amine modified product may have a structure in which an amine is modified with an aliphatic hydrocarbon group having 6 to 40 carbon atoms.

[0077] For details of the optionally substituted monovalent hydrocarbon group, the above explanation of (Optionally substituted monovalent hydrocarbon group) is incorporated herein.

[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) obtained by removing a predetermined number of atoms or atomic groups (e.g., hydrogen) from an amine compound. The amino group in the amine skeleton means a group selected from the group consisting of -NH2, -NH-, and -N(-)2, and also includes an amino group adjacent to a carbonyl group contained in an amide group, a urethane group, a urea group, an imide group, etc. Note that the amine skeleton may be an aliphatic group or an aromatic group having one or more amino groups, and does not exclude the presence of heteroatoms other than nitrogen.

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

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

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

[0083] The amine skeleton may be composed of a monovalent to trivalent amino group and a chain-like saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group which may be interrupted by an oxygen atom and / or a sulfur atom.

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

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

[0086] The amine modification has -Y N -Z N n The number may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, and is preferably 2 or more, and may be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1.

[0087] At least one -Y in the amine modification N -Z N n is bonded to the nitrogen atom of the amine skeleton. All -Y N -Z N n Among the number of -Y bonded to the nitrogen atom of the amine skeleton, N -Z N n The ratio of the number of -Y that is not bonded to a nitrogen atom of the amine skeleton may be 10% or more, 30% or more, 60% or more, 80% or more, or 100%, and may be 100% or less, 95% or less, 75% or less, 50% or less, or 25% or less. N -Z N n may be bonded to another group (eg, a hydrocarbon group) carried by the amine skeleton.

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

[0089] n is Y N Combined with Z N and may be an integer of 1 to 3. n may be 1 or more, 2 or more, or 3 or more, and may be 3 or less, 2 or less, or 1 or less, for example, 2 or less.

[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 may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more; and may be 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, or 300 or less.

[0092] Y N may have a carbonyl group. 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 groups selected from the group consisting of an amide group, a urea group, a urethane group, and an imide group together with the amino group in the amine skeleton. Examples of such an amide group, a urea group, a urethane group, and an imide group include -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'- -C(=O)-NR'- -C(=O)-NR'-C(=O)- [In the formula, R' is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).] Examples include: Y N is preferably attached to the nitrogen atom in the amine skeleton via a -(C=O)- group.

[0093] Y Nrepresents a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2, -N(-)2, a di- to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a di- to tetravalent hydrocarbon aromatic ring, and a di- to tetravalent heterocycle. [In the formula, R' is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).] It may be a 1+n valent group consisting of one or more groups selected from the group consisting of:

[0094] Y N is Y N1 and Y N2 is a 1+n valent group consisting of one or more selected from the group consisting of Y N1 is a group consisting of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2, and -N(-)2 (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms)); Y N2 is a group consisting of one or more selected from the group consisting of di- to tetravalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms, di- to tetravalent aromatic hydrocarbon rings, and di- to tetravalent heterocycles, In the present specification, Y N The group shown as is an amine skeleton on the left and a Z skeleton on the right. N Bind to.

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

[0096] Y N1 is a direct bond or a divalent or higher group. N1 The valence of Y may be 2 to 4, 2 to 3, or 2.N1 is preferably not only a direct bond.

[0097] Y N1 The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0098] Y N1 may be composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -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 (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms). Y N1 Examples include: direct binding, -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -C(=O)-NR'-C(=O)-, -C(=NR')-, -S-, -SO2-, -SO2NR'-, -C(OR')R'-, -C(OR')(-)2, -N(-)2 etc. [In the formula, R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).] In addition, Y N1is bonded to a nitrogen atom of the amine skeleton, the nitrogen atom is considered to be part of the amine skeleton (amino group).

[0099] 〇 Y N2 Y N2 is a linker of a hydrocarbon ring which may have a substituent, a hydrocarbon aromatic ring which may have a substituent, or a heterocycle which may have a substituent.

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

[0101] Y N2 is a divalent or higher group. Y N2 The valency of may be, for example, 2 to 4, 2 to 3, or 2.

[0102] Y N2 may have 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more; and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[0103] Y N2 is composed of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent aromatic hydrocarbon rings, and optionally substituted di- to tetravalent heterocycles.

[0104] The divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or straight chain hydrocarbon group. The divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group having 1 to 40 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more, and may be 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less. The valence of the aliphatic hydrocarbon group may be 2 or more, 3 or more, or 4, and may be 4 or less, 3 or less, or 2.

[0105] The aliphatic hydrocarbon group may have a substituent. Examples of the substituent include -OR', -N(R')2, -COOR', and a halogen atom (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms at each occurrence). The substituent may or may not have active hydrogen. The number of the substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the aliphatic hydrocarbon group having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0106] Examples of divalent to tetravalent hydrocarbon aromatic rings include groups obtained by removing 2 to 4 hydrogen atoms from a hydrocarbon aromatic ring such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthacene), pentacene, pyrene, and coronene. The number of ring-constituting atoms of the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12, and preferably 5 to 12. The valence of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, and may be 4 or less, 3 or less, or 2.

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

[0108] The divalent to tetravalent heterocycle may be an aliphatic group or an aromatic group. Examples of the divalent to tetravalent heterocycle include groups obtained by removing 2 to 4 hydrogen atoms from pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, etc. The number of ring-constituting atoms of the heterocycle is 3 to 20, 4 to 16, or 5 to 12, and preferably 5 to 12. The valence of the heterocycle may be 2 or more, 3 or more, or 4, and may be 4 or less, 3 or less, or 2.

[0109] The heterocycle may have a substituent. Examples of the substituent include -R', -OR', -N(R')2, -COOR', and halogen atoms (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms at each occurrence). The substituent may or may not have active hydrogen. The number of the substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the 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 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 include: -Ali- -Cy- -Ali(-)2 -Cy(-)2 (-)2Ali- (-)2Cy- (-)2Ali(-)2 (-)2Cy(-)2 -Ali-Cy- -Cy-Ali- -Cy-Ali-Cy- -Ali-Cy-Ali- [In the formula, Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and Cy is a hydrocarbon aromatic ring or heterocycle.] etc.

[0111] Y N2 Examples of specific examples include: -(CH2) p - (p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and having an unsaturated bond, a hydrocarbon group having a branched structure and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH2) q -Cy-(CH2) r -(q and r each independently represent an integer of 0 to 20, for example, 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle). etc.

[0112] Y N Example Y N In the following, R' is independently in each occurrence 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 An example of this is Y N If is bivalent, -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.

[0114] Y N An example of this is Y N If 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, In the amine-modified product, one or more Y N However, it is preferred that the terminal on the amine skeleton side is -(C=O)- and that the bond is with a 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 but, independently for each occurrence, direct binding, -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, or -C(=O)-NR'- -C(=O)-NR'-C(=O)- (In the formula, R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).) and 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). This makes it possible to impart good liquid repellency to the substrate.

[0118] Y N Further specific examples of the *-(C=O)- -O-(C=O)-NR'- [In the formula, * means bonding to a nitrogen atom of an amine skeleton, R' is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).] etc.

[0119] (Z N ) Z N represents an optionally substituted monovalent hydrocarbon group having 6 to 40 carbon atoms, and the above explanation of (Optionally substituted monovalent hydrocarbon group) is incorporated herein.

[0120] [Examples of amine modifications] (Amine modification example 1) Examples of amine modifications include those of the 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 [In the formula, Y N is independently in each occurrence a direct bond or a group with a valence of 1+n; Z N represents, independently in each occurrence, a linear or branched monovalent hydrocarbon group having from 6 to 40 carbon atoms which may have a substituent; L 1 represents, independently in each occurrence, a divalent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms which may be interrupted by an oxygen atom and / or a sulfur atom; n, independently in each occurrence, is an integer between 1 and 3, inclusive; p, in each occurrence, is an integer greater than or equal to 0 and less than or equal to 2; q, independently in each occurrence, is an integer greater than or equal to 0 and less than or equal to 2; p+q is the sum of each N(-Y N -Z N n ) p (-H) q In, 2, r is independently in each occurrence 0 or 1; s is independently in each occurrence 0 or 1; r+s is the sum of each N(-Y N -Z N n ) r (-H) s In, the sum of all p's and all r's is greater than or equal to 1; t is an integer between 0 and 10. The compound represented by the following formula (amine modified example 1) is exemplified.

[0121] In the amine modification example 1, YN , Z N For details of , and n, the above explanation is referred to.

[0122] In the amine modification example 1, L 1 L is a divalent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms, which may be interrupted by oxygen atoms and / or sulfur atoms, and may be a cyclic, branched, or straight-chain hydrocarbon group, and is preferably a straight-chain hydrocarbon group or an aromatic hydrocarbon. 1 The hydrocarbon group in the above description of the [amine skeleton] may be used as L, and the hydrocarbon group may be interrupted by oxygen atoms and / or sulfur atoms, or may consist of only carbon atoms, nitrogen atoms, and hydrogen atoms. 1 L may be, for example, a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 aromatic hydrocarbon rings. 1 is preferably a cyclic group having both a ring (e.g., an aromatic ring) and a chain structure (e.g., a straight-chain structure, ether oxygen, or thioether sulfur), and specific examples thereof include a 1,3-phenylenebisalkylene group, a 1,4-phenylenebisalkylene group, a diphenyletherdiyl group, and a diphenylthioetherdiyl group. 1 may have 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more carbon atoms; and may be 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, or 3 or less.

[0123] In the amine modification example 1, p, in each occurrence, is independently an integer between 0 and 2, inclusive; q, in each occurrence, is independently an integer between 0 and 2, inclusive; and p+q is equal to the sum of each N(-Y N -Z N n ) p (-H) q In the formula, p is 2. Preferably, p, independently at each occurrence, may be 1 or more, for example 2.

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

[0125] The sum of all p's and all r's is 1 or greater, i.e., the amine modification example 1 contains one or more -Y N -Z N n The sum of all p's and all r's may be 1 or more, 3 or more, 5 or more, 7 or more, 9 or more, 12 or more (the sum of all q's and all s's may be 0), or may be 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, or 4 or less.

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

[0127] (Amine modification example 2) Other examples of amine modifications include those of the 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 in each occurrence a direct bond or a group with a valence of 1+n; Z N represents, independently in each occurrence, a linear or branched monovalent hydrocarbon group having from 6 to 40 carbon atoms which may have a substituent; L2 represents an aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms and a valence of 1+u, which may be interrupted by an oxygen atom and / or a sulfur atom, n, independently in each occurrence, is an integer between 1 and 3, inclusive; p is an integer between 0 and 2, q is an integer between 0 and 2, p+q is 2, u is an integer between 1 and 3, The sum of p and u is greater than or equal to 1.] The compound represented by the following formula (amine modified example 2) is also included.

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

[0129] In the amine modification example 2, L 2 is an aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms and a valence of 1+u, which may be interrupted by oxygen atoms and / or sulfur atoms, and may be a cyclic, branched, or straight-chain hydrocarbon group, and is preferably a straight-chain hydrocarbon group or an aromatic hydrocarbon. 2 The hydrocarbon group in the above description of the [amine skeleton] may be used as L, and the hydrocarbon group may be interrupted by oxygen atoms and / or sulfur atoms, or may consist of only carbon atoms, nitrogen atoms, and hydrogen atoms. 2 L may be, for example, a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 aromatic hydrocarbon rings. 2 is preferably a cyclic group having both a ring (e.g., an aromatic ring) and a chain structure (e.g., a straight-chain structure, ether oxygen, or thioether sulfur), and specific examples thereof include a 1,3-phenylenebisalkylene group, a 1,4-phenylenebisalkylene group, a diphenyletherdiyl group, and a diphenylthioetherdiyl group. 2may have 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 the amine modification example 2, p is an integer of 0 to 2, q is an integer of 0 to 2, and p+q is 2. Preferably, p may be 1 or more, for example 2.

[0131] In the amine modification example 2, u is an integer of 1 to 3. u is 1, 2, or 3, for example, 2 or 3.

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

[0133] (Specific examples) Specific examples of the amine-modified product include compounds represented by the following formula: N is used as a reference.

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

[0142] [Manufacturing method] The method for producing the amine modified product is not limited, but may be carried out by reacting various amines (raw amines) with Z N A method of synthesis by reacting various amines with carboxylic acids containing Z groups. N and a synthesis method in which a group-containing carboxylic acid chloride, an acid anhydride, an isocyanate, etc. are reacted with the condensing agent may be a known condensing agent, and examples of the condensing agent include DCC, EDCI, CDI, BOP, COMU, DMT-MM, DPPA, and Py-Bop.

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

[0144] [Modified polyol] As an example of the liquid repellent compound, a modified polyol will be described below. The modified polyol 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 degree of polymerization of 1 or more. From the viewpoint of improving liquid repellency, the degree of polymerization of the polyol modified product may be 2 or more, 3 or more, 5 or more, 6 or more, preferably 7 or more, more preferably 8 or more, and even more preferably 9 or more, and from the viewpoint of improving the handleability of the repellent, it may be 100 or less, preferably 50 or less, more preferably 30 or less, and even more preferably 15 or less. The degree of polymerization means the number of repeating monomer units constituting the polymer.

[0146] The degree of polymerization in the present disclosure means an average degree of polymerization. The average degree of polymerization in the present disclosure means a degree of polymerization measured under the following conditions. In the present disclosure, when the polyol modified product is a polyglycerin modified product obtained by modifying polyglycerin, the degree of polymerization of the polyol modified product means the average degree of polymerization of the polyglycerin. The average degree of polymerization of polyglycerin is the average degree of polymerization (n) calculated from the hydroxyl value by the terminal group analysis method. In detail, the average degree of polymerization and the average molecular weight are calculated from the following formulas (Formula 1) and (Formula 2). (Formula 1) Average molecular weight=74n+18 (Equation 2) Hydroxyl value = 56110 (n + 2) / average molecular weight The hydroxyl value in the above formula (2) is a numerical value that is an index of the number of hydroxyl groups contained in polyglycerol. The hydroxyl value is calculated from the amount of potassium hydroxide required to neutralize the acetic acid required to acetylate the free hydroxyl groups contained in 1 g of polyglycerol, and is calculated in accordance with "Standard Methods for Analysis of Fats, Oils and Related Compounds (I), 2003 Edition, Established by the Japan Oil Chemists' Society." The hydroxyl value of the raw material polyglycerol is actually measured according to the above-mentioned Standard Methods for Analysis of Fats, Oils and Related Compounds, and the average degree of polymerization and average molecular weight of polyglycerol can be calculated from the above-mentioned formula.

[0147] In the present disclosure, when the polyol modified product is a polyvinyl alcohol modified product obtained by modifying polyvinyl alcohol, the degree of polymerization of the polyol modified product means the average degree of polymerization of the polyvinyl alcohol. The average degree of polymerization of polyvinyl alcohol can be measured in accordance with JIS K 6726 polyvinyl alcohol test method.

[0148] In the present disclosure, when the polyol-modified product is a polysaccharide-modified product obtained by modifying a polysaccharide, the degree of polymerization of the polyol-modified product means the average degree of polymerization of the polysaccharide. The average degree of polymerization of a polysaccharide can be analyzed as follows. The degree of polymerization is the number of monosaccharide units (fructose and glucose units) in the polysaccharide, and the average degree of polymerization is, for example, the average degree of polymerization determined by the top of the peaks of each analysis result obtained by a normal analysis method such as HPLC, GC, and HPAEC as follows. The measurement can be performed by using, for example, ULTRON PS-80N (8×300 mm) (solvent: water, flow rate: 0.5 ml / min, temperature: 50° C.) manufactured by Shinwa Chemical Industry Co., Ltd. or TSK-GEL G30000 PWXL (7.8×300 mm) (solvent: water, flow rate: 0.5 ml / min, temperature: 50° C.) manufactured by TOSOH Co., Ltd. as a column, and a differential refractometer as a detector.

[0149] The modified polyol may be low molecular weight (eg, weight average molecular weight less than 1500, less than 1000, 500 or less) and / or high molecular weight. The weight average molecular weight of the modified polyol may be 100 or more, 200 or more, 300 or more, 400 or more, 500 or more, 1000 or more, 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 30000 or more, or 500000 or more; and may be 1000000 or less, 750000 or less, 500000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 100000 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 hydroxyl group in the modified polyol may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 100%, preferably 10% or more, for example 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, particularly 80% or more, and may be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, 15% or less, for example 95% or less. Here, the "substitution rate" means the proportion (mol%) of the hydroxyl group derived from the polyol that is modified, and may mean the proportion (mol%) of the hydroxyl group that is modified with a monovalent hydrocarbon group having 6 to 40 carbon atoms that may have a substituent.

[0151] The residual rate of hydroxyl groups in the polyol modification may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, for example, 5% or more, and may be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, 15% or less, or 5% or less, for example, 50% or less, 30% or less, or 10% or less. Here, the "residual rate" refers to the proportion (mol%) of hydroxyl groups derived from the polyol that are not modified.

[0152] The number of modifying groups in the modified polyol may be 2 or more, 5 or more, 7 or more, 8 or more, 9 or more, 10 or more, 12 or more, 15 or more, 30 or more, or 50 or more, and may 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, and may be 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, or 400 or less. It is the value obtained by dividing the weight average molecular weight of the polyol modified product by the number of modifying groups. Here, the modifying group is preferably a monovalent hydrocarbon group which may have a substituent.

[0154] In the modified polyol, one or more hydroxyl groups of the polyol are substituted with 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 modified polyol may have a structure in which a polyol is modified with an aliphatic hydrocarbon group having 6 to 40 carbon atoms.

[0155] For details of the optionally substituted monovalent hydrocarbon group, the above explanation of (Optionally substituted monovalent hydrocarbon group) is incorporated herein.

[0156] (-Y O -Z O n ) In the present disclosure, modified polyols are those in which one or more of the hydroxy groups of the polyol has the formula: -Y O -Z O n [In the formula, Y O is Y O1 and Y O2 is a 1+n valent group consisting of one or more selected from the group consisting of Y O1 is a group consisting of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2, and -N(-)2 (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms)); Y O2 is a group consisting of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent aromatic hydrocarbon rings, and optionally substituted di- to tetravalent heterocycles, Z O represents a monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, n is an integer between 1 and 3. It may be substituted with a group represented by the following formula:

[0157] (Y O ) Y O is Y O1 and Y O2 is a 1+n valent group consisting of one or more selected from the group consisting of Y O1is a group consisting of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2, and -N(-)2 (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms)); Y O2 is a group composed of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent aromatic hydrocarbon rings, and optionally substituted di- to tetravalent heterocycles.

[0158] n is Y O Combined with Z O and may be an integer of 1 to 3. n may be 1 or more, 2 or more, or 3 or more, and may be 3 or less, 2 or less, or 1 or less, for example, 2 or less.

[0159] Y O The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more; and may be 3000 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less.

[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 sulfoneurea group, a sulfoneurethane group, or a sulfonimide group. For example, Y O may include -C(=O)-NR'-, -C(=S)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO2NR'-. O By including 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 divalent or higher group. O1 The valence of Y may be 2 to 4, 2 to 3, or 2. O1 is preferably not only a direct bond.

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

[0164] Y O1 may be composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -S(=O)2-, -NR'-, -C(OR')R'-, and -C(OR')(-)2 (wherein R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms). Y O1 Examples include: direct binding, -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO2-, -SO2NR'-, -C(OR')R'-, -C(OR')(-)2 etc. (In the formula, R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).) Examples include:

[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 sulfoneurea group, a sulfoneurethane group, or a sulfonimide group. For example, Y O2 may include -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO2NR'-. O1 By including these groups, the liquid repellency can be improved.

[0166] ○ Y O2 Y O2 is a linker of a hydrocarbon ring which may have a substituent, a hydrocarbon aromatic ring which may have a substituent, or a heterocycle which may have a substituent.

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

[0168] Y O2 is a divalent or higher group. O2 The valency of may be, for example, 2 to 4, 2 to 3, or 2.

[0169] Y O2 may have 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[0170] Y O2is composed of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent aromatic hydrocarbon rings, and optionally substituted di- to tetravalent heterocycles.

[0171] The divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or straight chain hydrocarbon group. The divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group having 1 to 40 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more, and may be 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less. The valence of the aliphatic hydrocarbon group may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0172] The aliphatic hydrocarbon group may have a substituent. Examples of the substituent include -OR', -N(R')2, -COOR', and a halogen atom (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms at each occurrence). The substituent may or may not have active hydrogen. The number of the substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the aliphatic hydrocarbon group having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0173] Examples of divalent to tetravalent hydrocarbon aromatic rings include groups obtained by removing 2 to 4 hydrogen atoms from a hydrocarbon aromatic ring such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthacene), pentacene, pyrene, and coronene. The number of ring-constituting atoms of the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12, and preferably 5 to 12. The valence of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0174] The aromatic hydrocarbon ring may have a substituent. Examples of the substituent include -R', -OR', -N(R')2, -COOR', and halogen atoms (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms at each occurrence). The substituent may or may not have active hydrogen. The number of the substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the aromatic hydrocarbon ring having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0175] The divalent to tetravalent heterocycle may be an aliphatic group or an aromatic group. Examples of the divalent to tetravalent heterocycle include groups obtained by removing 2 to 4 hydrogen atoms from pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, etc. The number of ring-constituting atoms of the heterocycle is 3 to 20, 4 to 16, or 5 to 12, and preferably 5 to 12. The valence of the heterocycle may be 2 or more, 3 or more, or 4, and may be 4 or less, 3 or less, or 2.

[0176] The heterocycle may have a substituent. Examples of the substituent include -R', -OR', -N(R')2, -COOR', and halogen atoms (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms at each occurrence). The substituent may or may not have active hydrogen. The number of the substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the heterocycle having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, for example, 65 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less.

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

[0178] Y O2 Examples of specific examples include: -(CH2) p - (p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and having an unsaturated bond, a hydrocarbon group having a branched structure and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH2) q -Cy-(CH2) r -(q and r each independently represent an integer of 0 to 20, for example, 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle). etc.

[0179] (Y O Example of Y O In the following, R' is independently in each occurrence 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).

[0180] Y O An example of this is Y O If is bivalent, -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 it 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.

[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.

[0184] (Preferred Y O Example of Preferably, Y O but -OY O11 -or -OY O11 -Y O21 -Y O12 - wherein each symbol represents independently 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-, -OC(=O)-, -OC(=O)-O-, -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO2-, -SO2NR'-, -C(OR')R'-, or -C(OR')(-)2. It may be.

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

[0186] Y O11 The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[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, which may be a hydrocarbon group having 1 to 40 carbon atoms.

[0189] Y O21 may have 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more; and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[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 (eg saturated) aliphatic hydrocarbon group.

[0191] Y O21 Examples of specific examples include: -(CH2) p - (p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and having an unsaturated bond, a hydrocarbon group having a branched structure and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH2) q -Cy-(CH2) r -(q and r each independently represent an integer of 0 to 20, for example, 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle). etc.

[0192] Y O12 may be -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO2-, -SO2NR'-, -C(OR')R'-, or -C(OR')(-)2.

[0193] Y O12 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 sulfoneurea group, a sulfoneurethane group, or a sulfonimide group. For example, Y O12 may be -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO2NR'-. C12 By including these groups, the liquid repellency can be improved.

[0194] (Z O ) ZO represents an optionally substituted monovalent hydrocarbon group having 6 to 40 carbon atoms, and the above explanation of (Optionally substituted monovalent hydrocarbon group) is incorporated herein.

[0195] [Other modifying groups] The hydroxy group of the polyol is -Y O -Z O n Examples of modifying groups are anionic and / or cationic groups.

[0196] The anionic group may be a monomer having a carboxyl group, a sulfonic acid group, or a phosphoric acid group.

[0197] Salts of anionic groups include alkali metal salts, alkaline earth metal salts, or ammonium salts, such as methylammonium salts, ethanolammonium salts, and triethanolammonium salts.

[0198] The cationic group is an amino group, preferably a tertiary amino group and a quaternary amino group. In the tertiary amino group, the two groups bonded to the nitrogen atom are preferably the same or different and are an aliphatic group having 1 to 5 carbon atoms (particularly an alkyl group), an aromatic group having 6 to 20 carbon atoms (aryl group), or an araliphatic group having 7 to 25 carbon atoms (particularly an aralkyl group, for example, a benzyl group (C6H5-CH2-)). In the quaternary amino group, the three groups bonded to the nitrogen atom are preferably the same or different and are an aliphatic group having 1 to 5 carbon atoms (particularly an alkyl group), an aromatic group having 6 to 20 carbon atoms (aryl group), or an araliphatic group having 7 to 25 carbon atoms (particularly an aralkyl group, for example, a benzyl group (C6H5-CH2-)). In the tertiary amino group and the quaternary amino group, the remaining group bonded to the nitrogen atom may have a carbon-carbon double bond. The cationic group may be in the form of a salt.

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

[0200] [Manufacturing method] The modified polyol may be prepared by reacting a modifying agent having a modifying group (or a precursor structure of the modifying group) with a hydroxy group of the polyol.

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

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

[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 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 be 1000 or less, 800 or less, 600 or less, 400 or less, 200 or less, 100 or less, or 75 or less. The hydroxy group equivalent of the polyol is the value obtained by dividing the weight average molecular weight of the polyol by the number of hydroxyl groups.

[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. The above natural products also include compounds converted from microorganisms. Examples of polyols include monosaccharides, oligosaccharides, polysaccharides, sugar alcohols (reducing sugars), hydroxy acids, amino acids, vitamins, flavonols, hydroxy hydrocarbons, hydroxy group-containing compound polymers, polyether polyols, polymer polyols, polyester polyols, and other polyols.

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

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

[0210] Examples of 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, isomaltodextrin, gellan gum, and tamarind seed gum.

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

[0213] Examples of amino acids include glucosamine.

[0214] Examples of vitamins include ascorbic acid and inositol.

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

[0216] Examples of hydroxyhydrocarbons include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, glycerin, trimethylolpropane, trimethylolethane, etc. Hydroxyhydrocarbons are hydrocarbons having a hydroxy group and may be aromatic or aliphatic, but are preferably aliphatic. Hydroxyhydrocarbons may also refer to hydroxyhydrocarbons other than compounds included in other groups such as polysaccharides (other hydroxyhydrocarbons).

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

[0218] An example of a polyether polyol may be a compound obtained by addition polymerization of an alkylene oxide to an initiator. Examples of initiators include compounds having a hydroxyl group with two or more functional groups. Examples of initiators include propylene glycol, polypropylene glycol, ethylene glycol, polyethylene glycol, glycerin, polyglycerin, trimethylolpropane, triethanolamine, pentaerythritol, ethylenediamine, aromatic diamine, diethylenetriamine, sorbitol, and sucrose. Examples of alkylene oxides include ethylene oxide and propylene oxide. Polyether polyols obtained by addition polymerization of an alkylene oxide to the above initiators are also called polyoxyalkylene polyols or oxyalkylene derivatives of polyols. Representative examples of polyether polyols include polyoxypropylene triols obtained by addition polymerization of propylene oxide to glycerin, and polyoxypropylene polyglyceryl ethers obtained by addition polymerization of propylene oxide to polyglycerin.

[0219] An example of a polymer polyol is a compound obtained by polymerizing at least a portion of a polyether polyol with an ethylenically unsaturated monomer, such as acrylonitrile or styrene.

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

[0221] (Modifier) The modifying agent is a compound that is reactive with a polyol and is preferably the above-mentioned compound having a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent.

[0222] Examples of modifying agents are as follows: Acid halide G(O=)CZ O Acid anhydride O(C(=O)-Z O )2 Carboxylic acid HO(O=)CZ O Isocyanate O=C=NZ O Thioisocyanate S=C=NZ O Epoxy (CH2OCH)CH2O-Z O Halide GZ O Amine H2N-Z O Hydroxy HO-Z O [In the formula, Z O is as defined above, and G is a halogen atom (e.g., F, Cl, Br, or I).

[0223] Z in the structure of the above modifier O may be replaced with any group constituting a 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 -Y O -Z O n It is also possible to use the following.

[0224] The modified polyol may be synthesized by reacting a polyol with a modifying agent. For example, a modified polyol can be synthesized by reacting a modifying agent that is an acid halide compound, an acid anhydride, or a carboxylic acid with a hydroxy group of a polyol to form an ester bond. Alternatively, a modified polyol can be produced by reacting a modifying agent that is a halide or an epoxy compound with a hydroxy group of a polyol to form an ether bond. Those skilled in the art can appropriately design the reaction conditions between the polyol and the modifying agent, such as using a catalyst (e.g., an acid catalyst or a base catalyst) or using a condensing agent, depending on the target product.

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

[0226] [Structure, etc.] The polycarboxylic acid modifications may be low molecular weight (eg, weight average molecular weight less than 1500, less than 1000, 500 or less) and / or high molecular weight. The weight average molecular weight of the 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, 30000 or more, or 500000 or more; and may 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, 100000 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 standard samples with the following apparatus and conditions. Separation column: SB-806M (8mm x 30mm, Shodex) Column temperature: 40℃ Mobile phase solvent: Ion-exchanged water Mobile phase flow rate: 1.0 mL / min Sample concentration: 0.5wt% Injection volume: 50μL 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) using tetrahydrofuran (THF) as an eluent and Shodex KF400RL and KF400RH columns (polystyrene gel) manufactured by Showa Denko K.K.

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

[0230] The residual ratio of hydroxyl groups of carboxyl groups 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 be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, 15% or less, or 5% or less, for example, 50% or less, 30% or less, or 10% or less. Here, the "residual ratio" refers to the ratio (mol%) of unmodified hydroxyl groups of carboxyl groups derived from polycarboxylic acid.

[0231] The number of modifying groups in the polycarboxylic acid modification 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 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 modifying group equivalent of the polycarboxylic acid modified product may be 150 or more, 250 or more, 350 or more, 450 or more, 550 or more, 650 or more, 750 or more, or 1000 or more, and may be 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, or 400 or less. It is the value obtained by dividing the weight average molecular weight of the polycarboxylic acid modified product by the number of modifying groups. Here, the modifying group is preferably a monovalent hydrocarbon group which may have a substituent.

[0233] In the modified polycarboxylic acid, one or more hydroxyl groups of the polycarboxylic acid are substituted with 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 modified polycarboxylic acid may have an aliphatic hydrocarbon group having 6 to 40 carbon atoms relative to the polycarboxylic acid.

[0234] For details of the optionally substituted monovalent hydrocarbon group, the above explanation of (Optionally substituted monovalent hydrocarbon group) is incorporated herein.

[0235] (-Y C -Z C n ) In the present disclosure, the modified polycarboxylic acid is a polycarboxylic acid in which the hydroxy group of one or more carboxyl groups is of the following formula: -Y C -Z C n [In the formula, Y C is Y C1 and Y C2 is a 1+n valent group consisting of one or more selected from the group consisting of Y C1is a group consisting of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2, and -N(-)2 (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms)); Y C2 is a group consisting of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent aromatic hydrocarbon rings, and optionally substituted di- to tetravalent heterocycles, Z C represents a monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, n is an integer between 1 and 3. It may be substituted with a group represented by the following formula:

[0236] (Y C ) Y C is Y C1 and Y C2 is a 1+n valent group consisting of one or more selected from the group consisting of Y C1 is a group consisting of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2, and -N(-)2 (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms)); Y C2 is a group composed of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent aromatic hydrocarbon rings, and optionally substituted di- to tetravalent heterocycles.

[0237] n is Y C Combined with Z Cand may be an integer between 1 and 3. n may be 1 or more, 2 or more, or 3 or more. n may be 3 or less, 2 or less, or 1 or less, for example, 2 or less.

[0238] Y C The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more; and may be 3000 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less.

[0239] Y C 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 sulfoneurea group, a sulfoneurethane group, or a sulfonimide group. For example, Y C may be -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO2NR'-. C By including 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. C1 The valence of Y may be 2 to 4, 2 to 3, or 2. C1 is preferably not only a direct bond.

[0242] Y C1 The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0243] Y C1may be composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -S(=O)2-, -NR'-, -C(OR')R'-, and -C(OR')(-)2 (wherein R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms). Y C1 Examples include: direct binding, -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO2-, -SO2NR'-, -C(OR')R'-, -C(OR')(-)2 etc. (In the formula, R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).) Examples include:

[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 sulfoneurea group, a sulfoneurethane group, or a sulfonimide group. For example, Y C1 may include -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO2NR'-. C1 By including these groups, the liquid repellency can be improved.

[0245] ○ Y C2 YC2 is a linker of a hydrocarbon ring which may have a substituent, a hydrocarbon aromatic ring which may have a substituent, or a heterocycle which may have a substituent.

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

[0247] Y C2 is a divalent or higher group. Y C2 The valency of may be, for example, 2 to 4, 2 to 3, or 2.

[0248] Y C2 may have 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more; and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[0249] Y C2 is composed of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent aromatic hydrocarbon rings, and optionally substituted di- to tetravalent heterocycles.

[0250] The divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or straight chain hydrocarbon group. The divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group having 1 to 40 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more, and may be 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less. The valence of the aliphatic hydrocarbon group may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0251] The aliphatic hydrocarbon group may have a substituent. Examples of the substituent include -OR', -N(R')2, -COOR', and a halogen atom (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms at each occurrence). The substituent may or may not have active hydrogen. The number of the substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the aliphatic hydrocarbon group having a substituent, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0252] Examples of divalent to tetravalent hydrocarbon aromatic rings include groups obtained by removing 2 to 4 hydrogen atoms from a hydrocarbon aromatic ring such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthacene), pentacene, pyrene, and coronene. The number of ring-constituting atoms of the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12, and preferably 5 to 12. The valence of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

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

[0254] The divalent to tetravalent heterocycle may be an aliphatic group or an aromatic group. Examples of the divalent to tetravalent heterocycle include groups obtained by removing 2 to 4 hydrogen atoms from pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, etc. The number of ring-constituting atoms of the heterocycle is 3 to 20, 4 to 16, or 5 to 12, and preferably 5 to 12. The valence of the heterocycle may be 2 or more, 3 or more, or 4, and may be 4 or less, 3 or less, or 2.

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

[0257] Y C2 Examples of specific examples include: -(CH2) p - (p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and having an unsaturated bond, a hydrocarbon group having a branched structure and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH2) q -Cy-(CH2) r -(q and r each independently represent an integer of 0 to 20, for example, 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle). etc.

[0258] (Y C Example of Y C In the following, R' is independently in each occurrence 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 An example of this is Y C If is bivalent, -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 --etc.

[0260] Y C An example of this is Y C If 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 -), 2, etc. can be mentioned.

[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.

[0263] (Preferred Y C Example of Preferably, Y C but -Y C11 -or -Y C11 -Y C21 -Y C12 - wherein each symbol represents independently at each occurrence: Y C11 is -O- or -NR'-, Y C21 is a hydrocarbon group having 1 to 40 carbon atoms, Y C12 is -O-, -OC(=O)-, -OC(=O)-O-, -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO2-, -SO2NR'-, -C(OR')R'-, or -C(OR')(-)2. It may be.

[0264] Y C11 is a non-hydrocarbon linker, which is a direct bond or a divalent or higher group.

[0265] Y C11 The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[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, which may be a hydrocarbon group having 1 to 40 carbon atoms.

[0268] Y C21 may have 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more; and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[0269] 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 (eg saturated) aliphatic hydrocarbon group.

[0270] Y C21 Examples of specific examples include: -(CH2) p - (p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and having an unsaturated bond, a hydrocarbon group having a branched structure and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH2) q -Cy-(CH2) r -(q and r each independently represent an integer of 0 to 20, for example, 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle). etc.

[0271] Y C12may be -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO2-, -SO2NR'-, -C(OR')R'-, or -C(OR')(-)2.

[0272] Y C12 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 sulfoneurea group, a sulfoneurethane group, or a sulfonimide group. For example, Y C12 may be -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO2NR'-. C12 By including these groups, the liquid repellency can be improved.

[0273] (Z C ) Z C represents an optionally substituted monovalent hydrocarbon group having 6 to 40 carbon atoms, and the above explanation of (Optionally substituted monovalent hydrocarbon group) is incorporated herein.

[0274] [Other modifying groups] The hydroxy group of the polycarboxylic acid is -Y C -Z C n The modified group may be substituted with a modifying group other than the above. Examples of the modifying group include an anionic group and / or a cationic group. The explanation of the [Other modifying groups] in the above polyol is applied to the anionic group and / or the cationic group.

[0275] [Manufacturing method] The polycarboxylic acid modification may be prepared by reacting a modifying agent having a modifying group (or a precursor structure of the modifying group) with a hydroxy group of the polycarboxylic acid.

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

[0277] The polycarboxylic acid may be a low molecular weight (e.g., weight average molecular weight less than 1000, 500 or less) and / or a polymer. 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 be 1000000 or less, 7500000 or less, 500000 or less, 3000000 or less, 100000 or less, 75000 or less, 500000 or less, 300000 or less, 100000 or less, 5000 or less, 30000 or less, 2000 or less, 1000 or less, or 500 or less.

[0278] The number of carboxyl groups in 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 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, or 150 or more, and may be 1000 or less, 800 or less, 600 or less, 400 or less, 200 or less, 100 or less, or 75 or less. The carboxyl equivalent of the polycarboxylic acid is the 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] Dicarboxylic acids are compounds 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, aldaric acid, and salts thereof.

[0283] Tricarboxylic acids are compounds having three carboxyl groups, such as citric acid, tricarballylic acid, t-aconitic acid, trimellitic acid, and salts thereof.

[0284] Tetracarboxylic acids are compounds having four carboxyl groups, such as pyromellitic acid and its salts.

[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 modifying agent is a compound that is reactive with polycarboxylic acid and is preferably the above-mentioned compound having a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent.

[0287] Examples of modifying agents are as follows: Epoxy (CH2OCH)CH2O-Z C Amine H2N-Z C Hydroxy HO-Z C [In the formula, ZC is as stated above.]

[0288] Z in the structure of the above modifier C may be replaced with any group constituting a 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 -Y C -Z C n It is also possible to use the following.

[0289] The modified polycarboxylic acid may be synthesized by reacting a polycarboxylic acid with a modifying agent. For example, a modifying agent that is an epoxy compound may be reacted with a carboxy group of a polycarboxylic acid to form an ester bond, thereby producing a modified polycarboxylic acid. Those skilled in the art can appropriately design the reaction conditions between the polycarboxylic acid and the modifying agent, such as by using a catalyst (e.g., an acid catalyst or a base catalyst) or a condensing agent, depending on the desired product.

[0290] [Dispersant] The repellent in the present disclosure may include 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] As the dispersant, an organic dispersant and an inorganic dispersant may be used separately, or an organic dispersant and an inorganic dispersant may be used in combination.

[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 fluorine-free.

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

[0295] The nonionic dispersant may be a low molecular weight or a high molecular weight dispersant. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may be 100,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

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

[0297] An example of an ether is a compound having an oxyalkylene group (preferably a polyoxyethylene group).

[0298] An example of the ester is an ester of an alcohol and a fatty acid. An example of the alcohol is a monohydric to tridehydric (particularly dihydric to decahydric) alcohol (e.g., an aliphatic alcohol) having 1 to 50 carbon atoms (particularly 10 to 30 carbon atoms). An example of the fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0299] An example of the ester ether is a compound in which an alkylene oxide (particularly ethylene oxide) is added to an ester of an alcohol and a fatty acid. An example of the alcohol is a monohydric to tridecahydric (particularly dihydric to decahydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms). An example of the fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0300] An example of an alkanolamide is formed from a fatty acid and an alkanolamine. The alkanolamide may be a monoalkanolamide or a dialkanolamine. An example of a fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. The alkanolamine may be an alkanol having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0301] The polyol may be a di- to penta-hydric alcohol having 10 to 30 carbon atoms. The amine oxide may be an oxide (eg, having 5 to 50 carbon atoms) of an amine (secondary amine or preferably tertiary amine).

[0302] The nonionic dispersant is preferably a nonionic dispersant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms in the alkylene group in the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic dispersant is generally preferably 2 to 100.

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

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

[0306] R 1R preferably has 8 to 20 carbon atoms, particularly preferably 10 to 18 carbon atoms. 1 Preferred specific examples include an octyl group, a nonyl group, a trimethylnonyl group, a lauryl group, a tridecyl group, an oleyl group, and a stearyl group. R 2 Examples are a propylene group and a butylene group. In the nonionic dispersant, p may be a number of 3 or more (for example, 5 to 200). q may be a number of 2 or more (for example, 5 to 200). That is, -(R 2 O) q may form a polyoxyalkylene chain. The nonionic dispersant may be a polyoxyethylene alkylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) in the center. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, and a styrene chain, and among these, an oxypropylene chain is preferred.

[0307] Examples of nonionic dispersants include ethylene oxide and hexylphenol, isooctatylphenol, hexadecanol, oleic acid, alkanes (C 12 -C 16 ) Thiol, Sorbitan Mono Fatty Acid (C7-C 19 ) or alkyl(C 12 -C 18 ) amines, etc., sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, lecithin derivatives, etc. Examples of nonionic dispersants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene polyoxybutylene alkyl ethers, polyoxyethylene polyoxypropylene glycol, polyethyleneimine ethoxylates, etc.

[0308] The proportion of the polyoxyethylene block may be 5 to 80% by weight, for example 30 to 75% by weight, particularly 40 to 70% by weight, based on the molecular weight of the nonionic dispersant (copolymer). The average molecular weight of the nonionic dispersant is generally 300 to 5,000, for example, 500 to 3,000. The nonionic dispersant may be a single type, or a mixture of two or more types. The nonionic dispersant may be a mixture of a compound having an HLB (hydrophilic-hydrophobic balance) of less than 15 (particularly 5 or less) and a compound having an HLB of 15 or more. Specifically, it is preferable to select from polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene, and polyoxypropylenes having an HLB value of 1 to 18, and sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene glycerin fatty acid esters, and polyoxyethylene sorbitan fatty acid esters having an HLB value of less than 7.

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

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

[0311] The cationic dispersant may be aliphatic or aromatic, and may be, for example, an ammonium salt (e.g., a quaternary ammonium salt). The cationic dispersant may be an oxyethylene adduct ammonium salt. Specific examples include amine salt-type dispersants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazoline; quaternary ammonium salt-type dispersants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzalkonium chloride, and benzethonium chloride; and polymer-type cationic dispersants such as polyquaternium-1 to 47. Examples of cationic dispersants include alkylamine salts and quaternary ammonium salts.

[0312] Low molecular weight cationic dispersants are R 21 -N + (-R 22 )(-R 23 )(-R 24 )X - [In the formula, R 21 , R 22 , R 23 and R 24 is hydrogen or a hydrocarbon group having 1 to 40 carbon atoms, X is an anionic group. R 21 , R 22 , R 23 and -R 24 Specific examples of X include alkyl groups (e.g., methyl, butyl, stearyl, and palmityl groups) and aromatic groups (e.g., benzyl and phenyl groups). Specific examples of X include halogens (e.g., chlorine) and acids (e.g., hydrochloric acid and acetic acid). Examples of cationic dispersants include monoalkyltrimethylammonium salts (alkyl having 4 to 40 carbon atoms) and benzalkonium chloride.

[0313] Specifically, the low molecular weight cationic dispersant is represented by the formula: R 1 p -N +R 2 q X - [In the formula, R 1 is C12 or higher (e.g. C 12 ~C 50 ) linear and / or branched aliphatic (saturated and / or unsaturated) groups, R 2 is H, a C1-4 alkyl group, a benzyl group, or a polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (particularly 2, particularly 3) to 50) (CH3 and C2H5 are particularly preferred), X is a halogen atom (e.g., chlorine), or a C1-C4 fatty acid salt, or a C1-C4 sulfonic acid salt; p is 1 or 2, q is 2 or 3, and p+q=4. R 1 may have 12 to 50 carbon atoms, for example, 12 to 30 carbon atoms.

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

[0315] The polymeric cationic dispersant may be any of various polymers (e.g., polyquaternium-1 to 47) having a cationic group (e.g., ammonium group, quaternary ammonium group). Examples of the polymeric cationic dispersant include cationic starch, cationic cellulose (e.g., O-(2-hydroxy-3-(trimethylammonio)propyl hydroxyethyl cellulose chloride), cationic guar gum, cationic xanthan gum, chitosan, and other cationic natural products (particularly cationic sugars); aziridine, vinylimidazole, aminoalkyl methacrylate, N,N,N',N'-tetramethyl-2-butene-1,4-diamine, quaternary dimethylammonium ethyl methacrylic acid, diallyldimethylammonium chloride, dimethylaminopropylamine, quaternary vinylimidazole, and other cationic group-containing monomer polymers.

[0316] [Anionic dispersant] The dispersant may comprise an anionic dispersant. The anionic dispersant may be an anionic surfactant. The dispersant may be free of an anionic dispersant.

[0317] The anionic dispersant may be a low molecular weight or a high molecular weight. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may be 100,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0318] Examples of anionic dispersants include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkanesulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfonic acid salts, N-acylamino acid type dispersants, phosphoric acid mono- or diester type dispersants, and sulfosuccinates. Examples of anionic dispersants include carboxylates (e.g., fatty acid salts).

[0319] [Amphoteric dispersant] The dispersant may comprise an amphoteric dispersant, which may be an amphoteric surfactant.

[0320] The amphoteric dispersant may be a low molecular weight or a high molecular weight dispersant. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may be 100,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0321] Examples of amphoteric dispersants include alanines, imidazolinium betaines, amido betaines, and betaine acetate. Specific examples include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylamino acetate betaine, and fatty acid amidopropyl dimethylamino acetate betaine.

[0322] [Inorganic dispersant] The dispersant may comprise 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 be 100 μm or less, 50 μm or less, 10 μm or less, 1 μm or less, 500 nm or less, or 300 nm or less. The average primary particle size can be measured, for example, by observation with a microscope (scanning electron microscope or transmission electron microscope). The inorganic dispersant may be a hydrophilic particle.

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

[0325] [Amount of dispersant] The amount of the dispersant may be, relative to 100 parts by weight of the liquid repellent compound, 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less.

[0326] [Liquid medium] The repellent of the present disclosure may include a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The repellent may be a dispersion or a solution. The repellent of the present disclosure may include 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 hydroxyl group (e.g., alcohol, polyols such as glycol-based solvents, ethers of polyols (e.g., monoethers), etc.). These may be used alone or in combination of two or more.

[0328] [Amount of liquid medium] The amount of the liquid medium may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 1 part by weight of the liquid repellent compound.

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

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

[0331] 〔wax〕 The repellent in the present disclosure may contain a wax. By containing a wax, it is possible to impart good liquid repellency to the substrate.

[0332] Examples of waxes include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin wax (polyethylene wax, polypropylene wax, etc.), oxidized polyolefin wax, silicone wax, animal and vegetable wax, mineral wax, etc. Paraffin wax is preferred. Specific examples of compounds constituting the wax include normal alkanes (e.g., tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane), and normal alkenes (e.g., 1-eicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane). The carbon number of the compound constituting the wax is preferably 20 to 60, for example, 25 to 45. The molecular weight of the wax may be from 200 to 2000, for example, from 250 to 1500, or from 300 to 1000. These may be used alone or in combination of two or more.

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

[0335] 〔silicone〕 The repellent in the present disclosure may contain silicone (polyorganosiloxane). By containing silicone, it is possible to obtain good texture and durability in addition to good liquid repellency.

[0336] As the silicone, known silicones can be used, and examples of silicones include polydimethylsiloxane and modified silicones (amino-modified, epoxy-modified silicone, carboxy-modified silicone, methylhydrogen silicone, etc.). The silicone may be a silicone wax having wax-like properties. These may be used alone or in combination of two or more.

[0337] The weight average molecular weight of the silicone may be 1,000 or more, 10,000 or more, or 50,000 or more, and may be 500,000 or less, 2,500,000 or less, 100,000 or less, or 50,000 or less.

[0338] [Amount of silicone] The amount of silicone may be, relative to 100 parts by weight of the liquid repellent compound, 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0339] [Organic acid] The repellent of the present disclosure may contain an organic acid. As the organic acid, a known one may be used. As the organic acid, carboxylic acid, sulfonic acid, sulfinic acid, etc. are preferably mentioned, and carboxylic acid is particularly preferable. As the carboxylic acid, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid, etc. are mentioned, and formic acid or acetic acid is particularly preferable. In the present disclosure, the organic acid may be used alone or in combination of two or more kinds. For example, formic acid and acetic acid may be used in combination.

[0340] [Amount of organic acid] The amount of the organic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the liquid repellent compound. The amount of the organic acid may be adjusted so that the pH of the repellent is 3 to 10, for example, 5 to 9, particularly 6 to 8. The repellent may be acidic (pH 7 or less, for example 6 or less).

[0341] [Inorganic acid] The repellent of the present disclosure may contain an inorganic acid. As the inorganic acid, a known one may 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, the inorganic acid may be used alone or in combination of two or more kinds. The stability of the aqueous dispersion can be improved by adding an inorganic acid.

[0342] [Amount of inorganic acid] The amount of the inorganic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the liquid repellent compound. The amount of the inorganic acid may be adjusted so that the pH of the repellent is 3 to 10, for example, 5 to 9, particularly 6 to 8. The repellent may be acidic (pH 7 or less, for example 6 or less).

[0343] [Hardening agent] The repellent of the present disclosure may include a curing agent (an active hydrogen reactive compound or an active hydrogen containing compound).

[0344] The curing agent (crosslinking agent) in the repellent can cure the repellent well. The curing 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 curing agent may include an isocyanate compound. The isocyanate compound may be a polyisocyanate compound. The polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound acts as a crosslinking agent. Examples of the polyisocyanate compound include aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates. The isocyanate compound may be a blocked isocyanate compound (e.g., a blocked polyisocyanate compound). The blocked isocyanate compound is a compound in which the isocyanate group of the isocyanate compound is masked with a blocking agent to suppress the reaction.

[0346] Examples of aliphatic polyisocyanates are trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-di ... Aliphatic diisocyanates such as cyanatomethyl caproate, and aliphatic triisocyanates such as lysine ester triisocyanate, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane, etc. These may be used alone or in combination of two or more.

[0347] Examples of alicyclic polyisocyanates include alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of alicyclic polyisocyanates include 1,3-cyclopentene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), and 1,3,5-triisocyanatocyclohexane. These may be used alone or in combination of two or more.

[0348] Examples of the araliphatic polyisocyanate are araliphatic diisocyanate and araliphatic triisocyanate.Specific examples of the araliphatic polyisocyanate are 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethylxylylene diisocyanate) or a mixture thereof, and 1,3,5-triisocyanatomethylbenzene.These may be used alone or in combination of two or more.

[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. These may be used alone or in combination of two or more.

[0350] Examples of the polyisocyanate derivatives include various derivatives of the above-mentioned polyisocyanate compounds, such as dimers, trimers, biurets, allophanates, carbodiimides, uretdione, uretoimine, isocyanurates, iminooxadiazinedione, etc. These may be used alone or in combination of two or more.

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

[0352] The blocking agent blocks free isocyanate groups. When the blocked polyisocyanate compound is heated to, for example, 100°C or higher, for example, 130°C or higher, the isocyanate group is regenerated and can easily react with the hydroxyl group. Examples of the blocking agent include phenol-based compounds, lactam-based compounds, aliphatic alcohol-based compounds, and oxime-based compounds. The polyisocyanate compounds can be used alone or in combination of two or more kinds.

[0353] The epoxy compound is a compound having an epoxy group. Examples of the epoxy compound include epoxy compounds having a polyoxyalkylene group, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether. The chloromethyl group-containing compound is a compound having a chloromethyl group. An example of the chloromethyl group-containing compound is chloromethyl polystyrene. The carboxyl group-containing compound is a compound having a carboxyl group. Examples of the carboxyl group-containing compound include (poly)acrylic acid and (poly)methacrylic acid.

[0354] Specific examples of the ketone group-containing compound include (poly)diacetone acrylamide and diacetone alcohol. Specific examples of the hydrazide compound include hydrazine, carbohydrazide, adipic acid hydrazide, and the like. Specific examples of the melamine compound include melamine resins and methyl etherified melamine resins.

[0355] [Amount of hardener] The amount of the curing agent may be, relative to 100 parts by weight of the liquid repellent compound, 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0356] [Other ingredients] The repellent may contain other components in addition to the above components. Examples of the other components include polysaccharides, paper strength agents, flocculants, retention aids, coagulants, binder resins, slip prevention agents, sizing agents, paper strength agents, fillers, antistatic agents, preservatives, ultraviolet absorbers, antibacterial agents, deodorants, fragrances, etc. These may be used alone or in combination of two or more. In addition to the above-mentioned components, other components include other water and / or oil repellents, dispersants, texture adjusters, softeners, flame retardants, paint fixing agents, anti-wrinkle agents, drying speed adjusters, crosslinking agents, film-forming agents, compatibilizers, antifreeze agents, viscosity adjusters, UV absorbers, antioxidants, pH adjusters, insect repellents, defoamers, shrink prevention agents, laundry wrinkle prevention agents, shape retention agents, drape retention agents, ironing improvers, whitening agents, whitening agents, fabric softening clay, dye transfer inhibitors such as polyvinylpyrrolidone, polymer dispersants, dirt removers, scum dispersants, fluorescent whitening agents such as 4,4-bis(2-sulfostyryl)biphenyl disodium (Ciba Specialty Chemicals' Chinopearl CBS-X), dye fixatives, and discoloration inhibitors such as 1,4-bis(3-aminopropyl)piperazine. The following can be blended: stain removers, enzymes such as cellulase, amylase, protease, lipase, keratinase, etc. as fiber surface modifiers, foam inhibitors, silk protein powders, their surface modified products or emulsified dispersions (e.g., K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemicals), hydrolyzed silk liquid (Jomo), Silkgen G Soluble S (Ichimaru Falcos)), stain prevention agents (e.g., nonionic polymer compounds consisting of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units (e.g., FR627 manufactured by GOO Chemical Industry Co., Ltd., SRC-1 manufactured by Clariant Japan, etc.), etc. These may be used alone or in combination of two or more.

[0357] [Amount of other ingredients] The amount or total amount of the other components may be, relative to 100 parts by weight of the liquid repellent compound, 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0358] <Pulp composition / pulp product manufacturing method> The pulp composition of the present disclosure can be obtained by treating a pulp substrate with a repellent agent comprising a liquid repellent compound.

[0359] The resulting pulp composition can be subjected to treatment steps such as drying, heating and molding, as necessary, to obtain a pulp product.

[0360] The repellent in the present disclosure can be applied to the pulp substrate as a treatment agent (particularly a surface treatment agent) by a conventionally known method. The treatment method may be a method in which the repellent in the present disclosure is dispersed and diluted in an organic solvent or water as necessary, and is attached to the inside and / or surface of the pulp substrate by a known method such as dip coating, spray coating, foam coating, etc., and then dried. The dilution ratio may be appropriately changed depending on the concentration and application of the repellent, but may be 3 to 2000 times, for example, 10 to 100 times. After drying, a pulp product to which the solid components of the repellent are attached is obtained. If necessary, the repellent may be applied together with an appropriate crosslinking agent and cured.

[0361] The repellent 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 repellent, the pulp substrate and the repellent may be mixed, or the solution may be applied or sprayed onto the pulp substrate. The treated pulp substrate is preferably dried and cured by heating to develop liquid repellency. The heating temperature may be, for example, 100°C to 200°C, 100°C to 170°C, or 100°C to 120°C. In the present disclosure, the heating time may be 5 seconds to 60 minutes, for example, 30 seconds to 3 minutes.

[0362] The pulp base material can be treated by an internal treatment method in which a repellent is added to the pulp base material (for example, in the form of a pulp slurry) before papermaking, or an external treatment method in which a repellent is applied to the pulp base material (for example, a pulp product) after papermaking. Examples of the internal treatment method include mixing, immersion, etc., and may include a step of adding a repellent to the pulp slurry and stirring and mixing. Examples of the external treatment method include spraying, coating, immersion treatment, foam coating, etc., and specifically include a pond type two-roll size press, a gate roll type, and a rod metering size press. The treatment may be an external treatment or an internal treatment. For example, when the pulp base material is paper, the paper may be coated with the repellent, or the solution may be attached or sprayed onto the paper, or the paper may be mixed with the pulp slurry before papermaking and treated. When the pulp base material is a fibrous material, the treatment method may include, for example, a padding treatment, a immersion treatment, a spray treatment, and a coating treatment. Examples of padding treatment include a method using a padding device described on pages 396-397 of Textile Dyeing and Processing Dictionary (published by Nikkan Kogyo Shimbun, 1963) and pages 256-260 of Color Dyeing Chemistry III (published by Jikkyo Publishing Co., Ltd., 1975). Examples of coating treatment include a method using a coating machine described on pages 473-477 of Dyeing and Finishing Equipment Directory (published by Sen-sha, 1981). Examples of immersion treatment include a method using a batch-type dyeing machine described on pages 196-247 of Dyeing and Finishing Equipment Directory (published by Sen-sha, 1981), and liquid flow dyeing machines, air flow dyeing machines, drum dyeing machines, winch dyeing machines, washer dyeing machines, cheese dyeing machines, etc. can be used. Examples of spray treatment include an air spray that sprays the treatment liquid in a mist form using compressed air, and a method using an air spray with a hydraulic atomization system.

[0363] The treatment method may be an internal addition treatment in which a repellent is added to the pulp slurry before papermaking. The internal addition treatment may include, but is not limited to, one or more of the following steps: a step of adding a repellent to the pulp slurry and stirring and mixing it; a step of suction-dehydrating the pulp composition prepared in the step through a mesh body of a predetermined shape to deposit the pulp composition to form a pulp molded intermediate; and a step of forming and drying the pulp molded intermediate using a heated mold to obtain a pulp molded product. The treated paper may be subjected to a heat treatment depending on the properties of the paper after simple drying at room temperature or at a high temperature. The temperature of the heat treatment may be 150°C or more, 180°C or more, or 210°C or more, and may be 300°C or less, 250°C or less, or 200°C or less, and may be particularly 80°C to 180°C. By performing the heat treatment in such a temperature range, excellent oil resistance and water resistance can be exhibited. The internally treated pulp base material may be treated with an externally added agent to deposit additional liquid repellent compounds on the surface.

[0364] The treatment method may be an external addition treatment in which a repellent is applied to the pulp base material after papermaking. The size press for external addition treatment can also be divided as follows according to the application method. One application method is a so-called pond type two-roll size press in which a coating liquid (sizing liquid) is supplied to a nip formed by passing paper between two rubber rolls, a coating liquid pool called a pond is created, and the paper is passed through this coating liquid pool to apply the sizing liquid to both sides of the paper. Other application methods are a gate roll type in which the sizing liquid is applied by a surface transfer type, and a rod metering size press. In the pond type two-roll size press, the sizing liquid is likely to penetrate into the inside of the paper, and in the surface transfer type, the sizing liquid components are likely to remain on the surface of the paper. In the surface transfer type, the coating layer is more likely to remain on the surface of the paper than in the pond type two-roll size press, and the coating layer formed on the surface is larger than in the pond type two-roll size press. In the present disclosure, performance can be imparted to the paper even when the former pond type two-roll size press is used. Papers thus treated may exhibit excellent oil and water resistance etc., optionally followed by a heat treatment which, depending on the nature of the paper, may range from 80°C to 180°C, for example up to 300°C, for example up to 200°C, after simple drying at room or elevated temperature.

[0365] Specific examples of pulp products include paper, paper containers, pulp molded products, food packaging materials, food containers, gypsum board base paper, coated base paper, medium quality paper, general liners and cores, neutral pure white roll paper, neutral liners, rust-proof liners and metal interleaving paper, kraft paper, neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper, and neutral information paper, etc. Suitable examples of pulp products include food packaging materials and food containers, and in particular pulp molded products for food contact applications.

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

[0367] The present disclosure will be described in detail below 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 ratio and median diameter (D50) of particles] For the liquid repellent compound and the aqueous dispersion, the volumetric abundance ratio of particles of 100 μm or more, the volumetric abundance ratio 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 using a laser diffraction / scattering device.

[0370] [Preparation Example 1: Preparation of decaglycerol dodecabehenyl ester dispersion] 2g of decaglycerol dodecabehenyl ester (polymerization degree 10, hydroxyl group substitution rate: 12 / 12*100 [100%], biobased ratio: 100%) as a polyol modification product, 0.2g of polyethylene oxide trimethyl nonyl ether (HLB: 13), and 17.8g of water were mixed to obtain precursor A of a water-dispersible repellent. This precursor A of a water-dispersible repellent was heated to 80°C and then stirred at 7000 rpm for 20 minutes with a homogenizer to obtain a water-dispersible repellent. The volumetric ratio of particles of 100μm or more in the obtained water-dispersible repellent was 0%, and the median diameter D50 was 19.8μm.

[0371] [Preparation Example 2: Preparation of ethylene bisstearic acid amide dispersion] 2 g of N,N'-ethylenebisstearic acid amide (biobased content: 97%, melting point: 143°C, ground particle size: 18 μm) that had been pulverized using a jet mill, 0.2 g of polyethylene glycol trimethyl nonyl ether (HLB13), and 17.8 g of water were mixed to obtain an aqueous dispersion composition (volume abundance 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 (biobased content: 95%, melting point: 145°C, ground particle size: 17 μm) that had been pulverized using a jet mill, 0.2 g of EO / PO polyalkylene glycol natural alcohol ether, and 17.8 g of water were mixed to obtain an aqueous dispersion composition (volume ratio of particles 100 μm or larger: 5%, volume median diameter: 17 μm).

[0373] [Preparation Example 4: Preparation of ethylene bis oleamide dispersion] 2 g of N,N'-ethylenebisoleamide (bio-based content: 96%, melting point: 116°C, ground particle size: 24 μm) that had been pulverized using a jet mill, 0.2 g of EO / PO polyalkylene glycol alcohol ether (HLB7), and 17.8 g of water were mixed to obtain an aqueous dispersion composition (volume ratio of particles 100 μm or larger: 0%, volume median diameter: 24 μm).

[0374] [Preparation Example 5: Preparation of xylylene bishydroxystearic acid amide dispersion] 2 g of N,N-xylylene-bis-12-hydroxystearylamide (biobased content: 83%, ground particle size: 9 μm) that had been pulverized using a jet mill, 0.2 g of polyethylene glycol trimethylnonyl ether (HLB13), and 17.8 g of water were mixed to obtain an aqueous dispersion composition (volume ratio of particles of 100 μm or more: 0%, volume median diameter: 9 μm).

[0375] [Preparation Example 6: Preparation of hexamethylene bishydroxystearic acid amide dispersion] 2 g of N,N'-hexamethylene-bis-12-hydroxystearylamide (bio-based content: 85%, melting point: 134°C, ground particle size: 12 μm) that had been pulverized using a jet mill, 0.2 g of EO / PO polyalkylene glycol natural alcohol ether, and 17.8 g of water were mixed to obtain an aqueous dispersion composition (volume ratio of particles of 100 μm or more: 3.5%, volume median diameter: 12 μm).

[0376] [Making pulp molds] Pulp mold was formed using an automatic molding machine. A mesh-like body was placed on a metal pulp mold mold with many suction holes at the bottom, and a metal tank was placed at the top, with a mixture of pulp slurry and water-dispersed repellent (pulp composition) being placed in the upper metal tank. The pulp composition was sucked and dehydrated through the pulp mold mold and mesh-like body by a vacuum pump from the side opposite to the side where the mesh-like body was placed in the pulp mold mold, and the solid content (pulp, etc.) contained in the pulp composition was deposited on the mesh-like body to obtain a pulp mold intermediate. Next, the obtained pulp mold intermediate was dried under a pressure of 0.05 to 5 MPa from above and below in a male-female metal mold heated to 60 to 250°C. This produced a pulp molded product molded into the shape of a container.

[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 removed from the pulp mold and the degree of soaking into the pulp mold was evaluated. The following evaluation values ​​were set according to the degree of soaking. 5: No stains on the inside. 4: Stain on the inside. No stain on the back. 3: Stain on the inside. Slight seepage on the back. 2: Stain on the inside. Less than 50% of the area has seeped through to the back. 1: Stain on the inside. Stain on the back is 50% or more but less than 100% of the area. 0: Seeping through to the entire back side.

[0378] <Example 1> An aqueous pulp slurry was prepared with a concentration of 0.5 wt%, containing 25% bagasse pulp and 75% wood pulp relative to the total amount of pulp. The decaglycerol dodecabehenyl ester dispersion of Preparation Example 1 was added to the pulp in a ratio of 3 wt% in terms of solid content to the pulp, to prepare a pulp composition. The pulp composition was placed in an automatic molding machine to prepare a pulp mold. An oil resistance test of the prepared pulp mold was conducted, and the oil resistance was 4 points. The results are shown in Table 1.

[0379] <Example 2> An aqueous pulp slurry was prepared with a concentration of 0.5 wt% containing 100% bagasse pulp relative to the total amount of pulp. The decaglycerol dodecabehenyl ester dispersion of Preparation Example 1 was added to the pulp in a ratio of 3 wt% in terms of solid content to the pulp to prepare a pulp composition. The pulp composition was placed in an automatic molding machine to prepare a pulp mold. An oil resistance test of the prepared pulp mold was conducted, and the oil resistance was 4 points. The results are shown in Table 1.

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

[0381] <Example 4> A pulp mold was produced in the same manner as in Example 1, except that a rosin sizing agent was added in an amount of 0.1 wt% relative to the pulp when preparing the pulp composition. An oil resistance test was carried out on the produced pulp mold, and the oil resistance 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 bisstearic acid amide dispersion of Preparation Example 2 was added to the pulp in a ratio of 2 wt% in terms of solid content to the pulp to prepare a pulp composition. A pulp mold was produced in the same manner and an oil resistance test was carried out, resulting in an oil resistance of 4 points. The results are shown in Table 1.

[0383] <Example 6> An aqueous pulp slurry was prepared in the same manner as in Example 1. The ethylene bishydroxystearic acid amide dispersion of Preparation Example 3 was added in a ratio of 3 wt% based on the pulp in terms of solid content to prepare a pulp composition. The pulp composition was placed in an automatic molding machine to prepare a pulp mold. A pulp mold was prepared in the same manner and subjected to an oil resistance test, resulting in an oil resistance of 4 points. The results are shown in Table 1.

[0384] <Example 7> An aqueous pulp slurry was prepared in the same manner as in Example 1. The ethylene bisoleamide dispersion of Preparation Example 4 was added to the pulp in a ratio of 7 wt% in terms of solid content to the pulp to prepare a pulp composition. A pulp mold was prepared in the same manner and an oil resistance test was carried out, resulting in an oil resistance of 4 points. The results are shown in Table 1.

[0385] <Example 8> An aqueous pulp slurry was prepared in the same manner as in Example 1. The xylylene bishydroxystearic acid amide dispersion of Preparation Example 5 was added to the pulp in a ratio of 2 wt% in terms of solid content to the pulp to prepare a pulp composition. A pulp mold was similarly prepared and an oil resistance test was carried out, resulting in an oil resistance of 4 points. The results are shown in Table 1.

[0386] <Example 9> An aqueous pulp slurry was prepared in the same manner as in Example 1. The hexamethylene bishydroxystearic acid amide dispersion of Preparation Example 6 was added in a ratio of 3 wt% based on the pulp in terms of solid content to prepare a pulp composition. A pulp mold was similarly produced and an oil resistance test was carried out, resulting in an oil resistance of 4 points. The results are shown in Table 1.

[0387] <Comparative Example 1> An aqueous pulp slurry with a concentration of 0.5 wt% containing 100% wood pulp relative to the total amount of pulp was prepared, and a pulp mold was produced in the same manner as in Example 1. 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.

[0388] <Comparative Example 2> An aqueous pulp slurry with a concentration of 0.5 wt% containing 100% wood pulp relative to the total amount of pulp 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 was prepared with a concentration of 0.5 wt% containing 100% bagasse pulp relative to the total amount of pulp. A sugar fatty acid ester dispersion (SEFOSE 1618U (Procter & Gamble Chemicals) was added to the pulp in a ratio of 3 wt% in terms of solid content, and a polyamine resin was added as a co-agent at 0.1 wt% relative to the pulp to prepare a pulp composition. The pulp slurry was placed in an automatic molding machine to produce a pulp mold. An oil resistance test was performed, and the oil resistance was scored as 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 relative to the total amount of pulp was prepared, and a pulp composition was prepared in the same manner as in Comparative Example 3. A pulp mold was produced and an oil resistance test was carried out, resulting in an oil resistance of 2 points. The results are shown in Table 1.

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

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

[0393] The results are summarized in the table below. [Table 1] TIFF2025076037000008.tif141164

Claims

1. A pulp composition comprising a liquid repellent compound and a pulp substrate, 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 glycosidic bond, The pulp composition, wherein the pulp base material comprises bagasse pulp.

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

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

4. The pulp composition according to claim 1, wherein the amount of the liquid repellent compound is from 0.5% to 25% by weight based on the pulp base material.

5. 2. The pulp composition according to claim 1, wherein the amount of the bagasse pulp in the pulp base material is from 20% by weight to 100% by weight.

6. The pulp composition of claim 1 , wherein the pulp composition comprises a dispersing agent.

7. The pulp composition of claim 1 , wherein the pulp composition comprises a paper chemical combination.

8. The pulp composition of claim 1 , wherein the pulp composition comprises a sizing agent.

9. The pulp composition of claim 1 , wherein the pulp composition comprises aluminum sulfate.

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

11. The molded pulp product according to claim 10, which is for food contact applications.

12. A method for producing a pulp composition, comprising treating a pulp substrate with a repellent comprising a liquid repellent compound, 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 glycosidic bond, The method for producing a pulp composition, wherein the pulp base material comprises bagasse pulp.

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

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