Pulp composition

Abstract

The present invention is a pulp composition containing a liquid-repellent compound and a pulp base material, the liquid-repellent compound being a compound containing a monovalent hydrocarbon group having 6 or more and 40 or less carbon atoms which can have a substituent, and not being a fatty acid ester having a glycoside bond, and the pulp base material containing bagasse pulp. With the pulp composition, a novel pulp composition having oil resistance and / or water resistance can be provided.

Description

Technical Field

[0001] This invention relates to pulp compositions, particularly pulp compositions having oil resistance and / or water resistance. Background Technology

[0002] Patent document 1 discloses a composition containing sugar fatty acid esters and hemicellulose or lignin that can be used to improve the barrier function of cellulose-based materials.

[0003] In the composition described in Patent Document 1, the sugar fatty acid ester is an essential component, and there are no studies on using other components to replace the sugar fatty acid ester. Furthermore, there is no disclosure that this composition exhibits excellent oil resistance or water resistance.

[0004] Existing technical documents Patent documents Patent Document 1: WO2021 / 019468 Summary of the Invention

[0005] The technical problem that the invention aims to solve The purpose of this invention is to provide a novel pulp composition with oil resistance and / or water resistance.

[0006] Technical means for solving technical problems The present invention includes the following methods.

[0007] [Item 1] A pulp composition comprising a liquid-repellent compound and a pulp substrate, The liquid-repellent compound is a compound containing a monovalent hydrocarbon group with 6 to 40 carbon atoms that may have substituents, and is not a fatty acid ester with a glycosidic bond. The pulp substrate contains bagasse pulp.

[0008] [Item 2] The pulp composition as described in Item 1, wherein, The liquid-repellent compound has at least one group selected from -OC(=O)R, -COOR, -NHCOR and -CONHR.

[0009] [In the formula, R is an independent hydrocarbon group with 6 to 40 monovalent carbon atoms that can have substituents.] [Item 3] The pulp composition as described in Item 1 or 2, wherein, The liquid-repellent compound is a compound modified with a hydrocarbon group having 6 to 40 carbon atoms that may have substituents, on an amine, polyol, or polycarboxylic acid.

[0010] [Item 4] The pulp composition as described in any one of items 1 to 3, wherein, The amount of the liquid-repellent compound relative to the pulp substrate is 0.5% to 25% by weight.

[0011] [Item 5] The pulp composition as described in any one of items 1 to 4, wherein, In the pulp substrate, the amount of bagasse pulp is more than 20% by weight and less than 100% by weight.

[0012] [Item 6] The pulp composition as described in any one of items 1 to 5, wherein, The pulp composition contains a dispersant.

[0013] [Item 7] The pulp composition as described in any one of items 1 to 6, wherein, The pulp composition contains paper-grade pharmaceuticals.

[0014] [Item 8] The pulp composition as described in any one of items 1 to 7, wherein, The pulp composition contains a sizing agent.

[0015] [Item 9] The pulp composition as described in any one of items 1 to 8, wherein, The pulp composition contains aluminum sulfate.

[0016] [Item 10] A pulp molded article obtained by molding the pulp composition of any one of items 1 to 9.

[0017] [Item 11] Pulp molded articles as described in Item 10, for use in food contact applications.

[0018] [Item 12] A method for manufacturing a pulp composition, comprising a step of treating a pulp substrate with a liquid-repellent agent containing a liquid-repellent compound. The liquid-repellent compound is a compound containing a monovalent hydrocarbon group with 6 to 40 carbon atoms that may have substituents, and is not a fatty acid ester with a glycosidic bond. The pulp substrate contains bagasse pulp.

[0019] [Item 13] A method for manufacturing the pulp composition as described in Item 12, wherein, The liquid-repellent compound has at least one group selected from -OC(=O)R, -COOR, -NHCOR and -CONHR.

[0020] [In the formula, R is an independent hydrocarbon group with 6 to 40 monovalent carbon atoms that can have substituents.] Invention Effects The pulp composition of the present invention has excellent oil resistance and / or water resistance. Detailed Implementation

[0021] <Definition of Terms> In this specification, "n-valent group" refers to a group having n valence bonds, that is, a group forming n bonds. Additionally, "n-valent organic group" refers to a carbon-containing n-valent group. There is no particular limitation on such organic groups; they can be hydrocarbon groups or their derivatives. Hydrocarbon derivatives refer to groups having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, halogen, or other groups at the end of the hydrocarbon group or in the molecular chain.

[0022] As used in this specification, "hydrocarbon group" is a group containing carbon and hydrogen, which is a group that has had a hydrogen atom removed from a hydrocarbon. There are no particular limitations on what constitutes such a hydrocarbon group; examples include C. 1－20 Hydrocarbon groups, such as aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The aforementioned "aliphatic hydrocarbon group" can be straight-chain, branched, or cyclic, and can be saturated or unsaturated. Furthermore, the hydrocarbon group can contain one or more ring structures. Where explicitly stated, the hydrocarbon group can be substituted by one or more substituents.

[0023] In this specification, whether or not the expressions "independent each time it appears", "independent of each other", "independent of each other" or the same are explicitly stated, unless otherwise stated, when a term (symbol) that may appear multiple times in a chemical structure is defined, the definition applies independently each time it appears.

[0024] It should be understood that the chemical structures described in this specification do not include chemical structures that are considered chemically impossible or extremely unstable by those skilled in the art.

[0025] <Pulp Composition> The pulp composition of the present invention contains a liquid-repellent compound and a pulp base material. The pulp composition of the present invention exhibits excellent oil resistance and / or water resistance, preferably both of these properties are excellent.

[0026] The pulp composition of the present invention can be obtained by adding a liquid-repellent compound to a pulp substrate. The pulp composition can be obtained by treating the pulp substrate with a liquid-repellent agent containing the liquid-repellent compound, wherein the amount or composition of the liquid-repellent agent can be adjusted to achieve the desired amounts of each component. Each component that may be included in the liquid-repellent agent can be added separately to the pulp composition as an additive.

[0027] The pulp composition of the present invention may be free of any compound selected from fluoroalkyl compounds having 8 or more carbon atoms, perfluoroalkyl compounds having 8 or more carbon atoms, fluoroalkyl compounds having 4 or more carbon atoms, perfluoroalkyl compounds having 4 or more carbon atoms, perfluoroalkyl compounds, fluoroalkyl compounds, and compounds containing fluorine atoms. Even without these fluorine compounds, the pulp composition of the present invention can impart liquid-repellent properties to the substrate.

[0028] The pH of the pulp composition can be 3 to 10, for example 5 to 9, especially 6 to 8, and the amount of each component can be adjusted to achieve such a pH.

[0029] [Pulp substrate] The pulp composition contains a pulp base material. The pulp base material is composed of pulp, which may be wood pulp, non-wood pulp, waste paper pulp, etc., and contains at least bagasse pulp.

[0030] [Wood pulp] As pulps, there are coniferous sulfate pulps obtained from fir and pine genera, and broadleaf sulfate pulps obtained from acacia, eucalyptus, beech, and poplar (e.g., poplar). Examples of coniferous sulfate pulps include unbleached coniferous sulfate pulp (NUKP), bleached coniferous sulfate pulp (NBKP), semi-bleached coniferous sulfate pulp (NSBKP), and coniferous sulfite pulp. Examples of broadleaf sulfate pulps include unbleached broadleaf sulfate pulp (LUKP), bleached broadleaf sulfate pulp (LBKP), semi-bleached broadleaf sulfate pulp (LSBKP), and broadleaf sulfite pulp. Furthermore, the pulps used can be used alone or in combination. In addition to sulfate pulp, there are also coniferous kraft pulp and hardwood kraft pulp, as well as mechanical pulps such as stone-milled pulp (SGP), pressure-milled stone-milled pulp (PGW), wood chip pulp (RGP), thermo-milled pulp (TGP), chemically milled pulp (CGP), groundwood pulp (GP), and thermomechanical pulp (TMP). Furthermore, as waste paper pulp, there are disintegrated waste paper pulp, disintegrated-deinked waste paper pulp, or disintegrated-deinked-bleached waste paper pulp made from brown waste paper, waste kraft paper envelopes, waste magazine paper, waste newspapers, waste leaflets, waste office paper, waste corrugated paper, waste white paper, waste drawing paper, waste handicraft paper, and waste land deeds.

[0031] [Non-wood pulp] Examples of non-wood pulps include pulps made from bagasse, kenaf, bamboo, cotton linters, cotton, linen, hemp, ramie, rice straw, thatch (Esparto), abaca, sisal, jute, flax, gampi, daphne, and paper mulberry.

[0032] [Pulp fiber length] Regarding the average fiber length of the pulp, from the viewpoint of improving oil resistance, it is preferably 0.1 mm or more, more preferably 0.3 mm or more, and even more preferably 0.5 mm or more. Furthermore, from the viewpoint of ease of manufacture, 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.

[0033] [Pulp fiber width] Regarding the average fiber diameter of the pulp, from the viewpoint of improving oil resistance, it is preferably 5 μm or more, more preferably 10 μm or more, and even more preferably 15 μm or more, and preferably 50 μm or less, more preferably 40 μm or less, and even more preferably 30 μm or less.

[0034] [Composition of pulp substrate] In the pulp base material, the amount of bagasse pulp can exceed 0% by weight, be 10% or more by weight, 20% or more by weight, 30% or more by weight, 40% or more by weight, 50% or more by weight, 60% or more by weight, or 70% or more by weight, preferably 20% or more by weight; and can be less than 100% by weight, less than 90% by weight, less than 80% by weight, less than 70% by weight, less than 60% by weight, less than 50% by weight, less than 40% by weight, less than 30% by weight, less than 20% by weight, or less than 10% by weight, for example, less than 80% by weight.

[0035] In the pulp base material, the total amount of pulp other than bagasse can be more than 0% by weight, more than 10% by weight, more than 20% by weight, more than 30% by weight, more than 40% by weight, more than 50% by weight, more than 60% by weight, or more than 70% by weight, and can be less than 99% by weight, less than 90% by weight, less than 80% by weight, less than 70% by weight, less than 60% by weight, less than 50% by weight, less than 40% by weight, less than 30% by weight, less than 20% by weight, or less than 10% by weight.

[0036] In the pulp substrate, the amount of wood pulp can be 0% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, or 70% or more, and can be less than 99% or less, 90% or less, 80% or less, 70% or less, 60% or less, 50% or less, 40% or less, 30% or less, 20% or less, or 10% or less.

[0037] [Morphology of pulp substrate] The pulp substrate when adding a liquid-repellent compound can be in the form of pure pulp, pulp stock, pulp products, etc. For specific examples, it can be listed as: bleached or unbleached chemical pulp such as sulfate pulp or sulfite pulp, bleached or unbleached high-yield pulp such as groundwood pulp, mechanical pulp or thermomechanical pulp, etc.; pulp stock containing the above pulps; pulp products such as paper, paper containers, and pulp molded products.

[0038] [Amount of pulp substrate] In the pulp composition, the amount of pulp base material can 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 can 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 pulp base material in the pulp composition can be 30% by weight or less; when the pulp composition is prepared by external addition, the amount of pulp base material in the pulp composition can be 75% by weight or more.

[0039] In pulp compositions other than liquid media, the amount of pulp base material can be 50% or more by weight, 60% or more by weight, 70% or more by weight, 80% or more by weight, 90% or more by weight, 95% or more by weight, or 99% or more by weight, and can be less than 99.9% by weight, less than 95% by weight, less than 90% by weight, less than 85% by weight, less than 75% by weight, less than 65% by weight, or less than 55% by weight.

[0040] [Liquid medium] The pulp composition may contain a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent, typically an aqueous medium, especially water. The liquid medium may include a liquid medium derived from an additive.

[0041] [Amount of liquid medium] In the pulp composition, the amount of liquid medium can 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 can be less than 99% by weight, less than 75% by weight, less than 50% by weight, less than 40% by weight, less than 30% by weight, less than 20% by weight, less than 10% by weight, less than 5% by weight, less than 4% by weight, or less than 3% by weight. Typically, when the pulp composition is prepared by internal addition, the amount of liquid medium in the pulp composition can be 50% by weight or more, particularly 90% by weight or more; when the pulp composition is prepared by external addition, the amount of liquid medium in the pulp composition can be less than 30% by weight, particularly less than 10% by weight.

[0042] [Liquid-repellent compounds] The pulp composition contains a liquid-repellent compound. For details regarding the types of liquid-repellent compounds, please refer to the description of liquid-repellent compounds in the section on liquid-repellent agents.

[0043] [Amount of the liquid-repellent compound] The amount of the liquid-repellent compound relative to the pulp substrate can 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 can 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.

[0044] The amount of the liquid-repellent compound as an amine modifier relative to the pulp substrate can 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 can 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.

[0045] The amount of the liquid-repellent compound used as a polyol modifier relative to the pulp substrate can 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 can 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.

[0046] The amount of the liquid-repellent compound as a polycarboxylic acid modifier relative to the pulp substrate can 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 can 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.

[0047] Liquid-repellent compounds can be used to externally treat the surface of pulp substrates (such as paper, paper containers, pulp molded products, and other pulp products). The amount of liquid-repellent compound contained in the coating layer formed by this external treatment can be as low as 0.01 g / m³. 2 Above, 0.03g / m 2 Above, 0.05g / m 2 Above, 0.1g / m 2 Above, 0.3g / m 2 Above, 0.5g / m 2 Above or 1.0g / m 2 The above, and can be 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 Below or 0.1g / m 2 the following.

[0048] [Dispersant] Pulp compositions may contain dispersants. For details on the types of dispersants, please refer to the description of dispersants in the section on dispersants.

[0049] [Amount of dispersant] The amount of dispersant relative to the pulp substrate can 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 can 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, preferably 5.0% by weight or less, more preferably 3.0% by weight or less.

[0050] [Paper strength enhancer] Pulp compositions may contain paper strength enhancers. Examples of paper strength enhancers include: Cationic polyacrylamide, anionic polyacrylamide, amphoteric polyacrylamide, and other polyacrylamide-based paper strength enhancers; Starch, enzyme-modified starch, thermochemically modified starch, oxidized starch, esterified starch, etherified starch (e.g., hydroxyethylated starch), aldehyde starch, cationic starch, starch, xanthan gum, ebony gum, vinylon gum, guar gum, pectin, tamarind gum, carrageenan, chitosan, gum arabic, locust bean gum, cellulose, alginic acid, agar, dextran, cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, chitin nanofibers, cellulose nanofibers and pullulan, and their modified polysaccharides (e.g., modified polysaccharides with hydroxyl or cationic groups) are all polysaccharide-based paper strength reinforcing agents. Polyamide-based paper strength reinforcing agents, such as polyamide resin, polyamine resin, polyamide-polyamine resin, polyamide-epoxychlorohydrin resin, polyamide-polyamine-epoxychlorohydrin resin, polyamide-polyurea-formaldehyde resin, and epoxy polyamide resin; Urea / melamine-based paper strength enhancers, such as urea resin, melamine resin, urea-formaldehyde resin, and melamine-formaldehyde resin. Polyvinyl alcohol (PVA) is a type of paper strength reinforcing agent, including fully saponified PVA, partially saponified PVA, carboxyl-modified PVA, silanol-modified PVA, cationic-modified PVA, and terminal alkyl-modified PVA. Styrene-butadiene copolymer, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, polyacrylate, fatty acid diamide, polyethyleneimine resin, ketone-aldehyde resin, etc.

[0051] As the paper strength enhancer of the present invention, polyacrylamide-based paper strength enhancers, polysaccharide-based paper strength enhancers, or polyamide-based paper strength enhancers are preferred.

[0052] [Amount of paper strength enhancer] The amount of paper strength enhancer relative to the pulp can 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 can 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.

[0053] [Sizing agent] The pulp composition may contain a sizing agent. Examples of sizing agents include cationic sizing agents, anionic sizing agents, neutral sizing agents, amphoteric sizing agents, such as rosin-based sizing agents (e.g., acidic rosin-based sizing agents, neutral rosin-based sizing agents), alkyl ketone dimers, alkenyl succinic anhydride, etc.

[0054] [Amount of sizing agent] The amount of sizing agent relative to pulp can 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 can be less than 10% by weight, less than 7.5% by weight, less than 5.0% by weight, less than 4.0% by weight, less than 3.0% by weight, less than 2.0% by weight, less than 1.0% by weight, less than 0.75% by weight, or less than 0.5% by weight.

[0055] [Other additives] In addition to the components mentioned above, pulp compositions may also contain fixatives (such as aluminum sulfate), coagulants-coagulants (such as polyamine resins), retention aids (such as polyacrylamide resins), organic acids (such as formic acid and acetic acid), dyes, adhesive control agents, defoamers, and other known paper-specific agents that can be used in the manufacture of pulp products, as well as other additives.

[0056] [Amount of other additives] The amounts of other additives relative to the pulp base material can be 0.01% by weight or more, 0.1% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, and can be less than 30% by weight, less than 20% by weight, less than 10% by weight, less than 5% by weight, less than 3% by weight or less than 1% by weight.

[0057] <Dispensing Agent> The repellent of the present invention adheres to a substrate (especially a pulp substrate) and can impart liquid-repellent properties to the substrate, such as water resistance, oil resistance, water repellency, oil repellency and / or stain resistance. It can also function as a water-resistant agent, oil-resistant agent, water-repellent agent, oil-repellent agent and / or stain-resistant agent.

[0058] The applicator of the present invention contains a liquid-repellent compound as an active ingredient. The liquid-repellent compound can be used as an applicator on its own, or in combination with other ingredients described below.

[0059] The repellent of the present invention may be free from any compound selected from fluoroalkyl compounds having 8 or more carbon atoms, perfluoroalkyl compounds having 8 or more carbon atoms, fluoroalkyl compounds having 4 or more carbon atoms, perfluoroalkyl compounds having 4 or more carbon atoms, perfluoroalkyl compounds, fluoroalkyl compounds, and compounds having fluorine atoms. Even without these fluorine compounds, the repellent of the present invention can impart liquid-repellent properties to the substrate.

[0060] In the dispersant of the present invention, the volume percentage of particles larger than 100 μm, as measured by laser diffraction scattering, can 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 can be less than 50%, less than 30%, less than 20%, less than 15%, less than 10%, less than 5%, less than 3%, or less than 1.5%. The method for setting the volume percentage of particles larger than 1 μm, as measured by laser diffraction scattering, within the above range is not limited; for example, a pulverizer or homogenizer can be used to refine the particles in the raw materials and / or dispersion.

[0061] The median particle size of the dispersant in this invention, measured by laser diffraction scattering, can be 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.2 μm or more, 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, 0.6 μm or more, 1.0 μm or more, 5.0 μm or more, 10.0 μm or more, 20.0 μm or more, 30.0 μm or more, 40.0 μm or more, 50.0 μm or more, 75.0 μm or more, or 100.0 μm. The particle size can be 100 μm or less, 90 μm or less, 80 μm or less, 70 μm or less, 60 μm or less, 50 μm or less, 40 μm or less, 30 μm or less, 20 μm or less, 10 μm or less, 5 μm or less, 3 μm or less, 1 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, 0.3 μm or less, or 0.2 μm or less, preferably 1 μm or less. In this invention, the volume median particle size refers to the median particle size (D50) in the particle size distribution of the volume reference obtained by laser diffraction scattering method.

[0062] The average particle size obtained from scanning electron microscopy images of particles obtained by removing the liquid medium from an agent (e.g., an oil-resistant agent for pulp) used in the present invention as a water-dispersible composition by natural drying at room temperature can 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 can 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 achieve a particle size within the above range, particles in the raw material and / or dispersion can be finely refined, for example, using a pulverizer or homogenizer. Room temperature refers to 20°C to 30°C, particularly 25°C.

[0063] The ionic charge density of the dispersant of the present invention can 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 -40 μeq / g or more. The ionic charge density of the repellent of the present invention is 0 μeq / g or more, -200 μeq / g or more, or -50 μeq / g or more; and may be 5000 μeq / g or less, 2500 μeq / g or less, 1000 μeq / g or less, 750 μeq / g or less, 500 μeq / g or less, 400 μeq / g or less, 350 μeq / g or less, 300 μeq / g or less, 200 μeq / g or less, 100 μeq / g or less, or 50 μeq / g or less, preferably 1000 μeq / g or less, more preferably 500 μeq / g or less, for example, 300 μeq / g or less. The ionic charge density of the repellent of the present invention is particularly preferably -600 μeq / g or more and 100 μeq / g or less. The ionic charge density of the repellent of the present invention can be determined, for example, by the following method.

[0064] For a sample solution with a solid component of 0.1 g / L, the anion requirement is determined using a 1 / 1000 equivalent concentration of potassium polyvinyl sulfonate solution with a particle charge meter (BTG MUTEK PCD-06), and the ionic charge density (cation charge density) is calculated using the following formula (1). Alternatively, a polydiallyldimethylammonium chloride solution is used instead of potassium polyvinyl sulfonate, and the cation requirement is determined in the same manner, and the ionic charge density (anion charge density) is calculated using the following formula (1).

[0065] Ion charge density (μeq / g) = A / B (1) A: Cation requirement or anion requirement (μeq / L) B: Sample solution concentration (g / L).

[0066] [Liquid-repellent compounds] The liquid-repellent compound of the present invention adheres to a substrate (especially a pulp substrate) and can impart liquid-repellent properties, such as water resistance, oil resistance, water repellency, oil repellency and / or stain resistance, to the substrate.

[0067] [Characteristics, etc.] The following describes the properties that liquid-repellent compounds can possess.

[0068] The HD (n-hexadecane) contact angle of the liquid-repellent compound can 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 can be 100° or less, 90° or less, or 75° or less. By having an HD contact angle of the liquid-repellent compound at or above the lower limit mentioned above, the substrate can be effectively imparted with liquid-repellent properties (especially oil-repellent properties). The HD contact angle is the static contact angle of the spin-coated film of the liquid-repellent compound, which is the value obtained by dropping 2 μL of HD onto the spin-coated film and measuring the contact angle after 1 second.

[0069] The water contact angle of a liquid-repellent compound can be greater than 35°, greater than 40°, greater than 45°, greater than 50°, greater than 55°, greater than 65°, greater than 75°, greater than 85°, greater than 90°, or greater than 100°, and can be less than 160°, less than 140°, less than 130°, less than 120°, less than 110°, less than 100°, or less than 90°. By having a water contact angle of greater than or equal to the lower limit mentioned above, the liquid-repellent compound can effectively impart liquid-repellent properties (especially water-repellent properties) to the substrate. The water contact angle is the static contact angle of a spin-coated film of a liquid-repellent compound, which is the value obtained by adding 2 μL of water to the spin-coated film and measuring the contact angle after 1 second.

[0070] The repellent compound is preferably a bio-based compound containing bio-based carbon. The bio-based content is determined according to ASTM D6866. The bio-based content can be 20% or more, preferably 30% or more, more preferably 50% or more, further preferably 60% or more, even more preferably 70% or more, and most preferably 80% or more or 90% or more, for example, 100%. A high bio-based content means less use of fossil resources such as petroleum; from this perspective, it can be said that the higher the bio-based content of the repellent compound, the better.

[0071] The biodegradability of the liquid-repellent compound at 180 days preferably has a biodegradability of 5% or more. From the perspective of reducing environmental impact, the higher the biodegradability, the better. The biodegradability of the liquid-repellent compound at 180 days can 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, further preferably 70% or more, and most preferably 80% or more. The biodegradability of the liquid-repellent compound at 60 days preferably has a biodegradability of 5% or more. From the perspective of reducing environmental impact, the higher the biodegradability, the better. The biodegradability of the liquid-repellent compound at 60 days can 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. The biodegradability can be as specified in JIS K 6953-1 or ASTM D6400.

[0072] The melting point of the liquid-repellent compound can be above 30°C, above 40°C, above 60°C, above 80°C, above 100°C, or above 120°C, preferably above 40°C; and can be below 250°C, below 225°C, below 200°C, below 150°C, below 130°C, below 120°C, below 110°C, below 100°C, below 80°C, or below 50°C.

[0073] [Structure, etc.] The liquid-repellent compound of the present invention may not have any one of the following groups selected from fluoroalkyl groups with 8 or more carbon atoms, perfluoroalkyl groups with 8 or more carbon atoms, fluoroalkyl groups with 4 or more carbon atoms, perfluoroalkyl groups with 4 or more carbon atoms, perfluoroalkyl groups, fluoroalkyl groups, and fluorine atoms. Even without these fluorine-containing groups, the liquid-repellent compound can impart liquid-repellent properties to the substrate.

[0074] Liquid-repellent compounds can be compounds containing a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have substituents. From the viewpoint of liquid repellency, liquid-repellent compounds can have a hydrocarbon group having 6 to 40 carbon atoms (e.g., an aliphatic hydrocarbon group).

[0075] (Can be a monovalent hydrocarbon group with substituents) Liquid-repellent compounds can have a monovalent hydrocarbon group, which can have substituents.

[0076] The hydrocarbon group can be a monovalent hydrocarbon group with 6 to 40 carbon atoms. The hydrocarbon group can be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and is particularly preferred to be an aliphatic hydrocarbon group. The hydrocarbon group can be branched, cyclic, or linear, and is more preferably linear.

[0077] The number of carbon atoms in the hydrocarbon group can 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 can 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.

[0078] The hydrocarbon group may have substituents, but is preferably unsubstituented. Examples of substituents include -OR', -N(R')2, -COOR', and halogen atoms (where R' is independently a hydrocarbon group with 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms each time it appears). Substituents may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the hydrocarbon group with substituents, the amount of carbon atoms 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, relative to the amount of carbon atoms and heteroatoms; 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 (e.g., 1) -OR' (especially -OH) as substituents (e.g., at positions other than the terminal).

[0079] The liquid-repellent compound of the present invention is preferably not a fatty acid ester having a glycosidic bond. A fatty acid ester having a glycosidic bond is typically a compound in which a fatty acid is added to the hydroxyl group of a compound having a glycosidic bond structure (typically a sugar (monosaccharide or polysaccharide)) via an ester bond. Using such a fatty acid ester is not preferred because the liquid-repellent properties are reduced.

[0080] [Examples of liquid-repellent compounds] Examples of liquid-repellent compounds include compounds having a hydrocarbon group having 6 to 40 carbon atoms. Examples and preferred ranges of hydrocarbon groups are as described above.

[0081] The liquid-repellent compound can be a compound having at least one group selected from -O(C=O)R, -COOR, -NHCOR and -CONHR [where R is a hydrocarbon group with 6 to 40 carbon atoms that can be monovalent and have substituents].

[0082] Liquid-repellent compounds may contain ester, amide, urethane, urea, imide, thioamide, thiourethane, thiourea, thioimide, sulfonamide, sulfonurea, sulfonamide, or sulfonimide (e.g., ester, amide, urethane, urea, imide). For example, liquid-repellent compounds may contain -C(=O)-O-, -O-C(=O)-, -C(=O)-NR'-, -O-C(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'-, or -SO2NR'- (where 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) each time it appears). Liquid-repellent compounds can be compounds formed by bonding a starting compound with a modifying group (especially a monovalent hydrocarbon group that may have substituents, as mentioned above) through at least one of these groups. Liquid-repellent compounds may contain an amide structure. By including at least an amide structure, the liquid-repellent property is enhanced. Here, the amide structure can be a broad amide structure, selected from amide (acid amide) groups, urethane groups, urea groups, imide groups, thioamide groups, thiourethane groups, thiourea groups, thioimide groups, sulfonamide groups, sulfonamide groups, sulfonamide groups, sulfonamide groups, sulfonimide groups, etc. The amide structure can be selected from -(C=O)N(-)2, -(C=S)N(-)2, and -S(=O)2N(-)2 (wherein the orientation of each group can be reversed). Here, at least one of the valence bonds of the N in the amide structure can be bonded to a hydrogen atom. The preferred amide structure is -(C=O)N(-)2, which can be an amide structure selected from amide, urethane, urea and imide groups.

[0083] As more specific examples of the aforementioned liquid-repellent compounds, compounds modified with hydrocarbon groups having 6 to 40 carbon atoms, which may have substituents, can be listed. In this specification, these are also referred to as amine-modified, polyol-modified, and polycarboxylic acid-modified compounds, respectively, and will be described in detail elsewhere.

[0084] [Amount of the liquid-repellent compound] In the repellent, the amount of the repellent compound can 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, or 30% by weight or less, and can also be less than 60% by weight, less than 50% by weight, less than 40% by weight, less than 30% by weight, less than 20% by weight, less than 10% by weight, less than 5% by weight, or less than 3% by weight. The repellent compound can be used alone as a repellent.

[0085] [Amine-modified form] As an example of a liquid-repellent compound, an amine-modified compound will be described. An amine-modified compound is a compound that has been chemically modified to exhibit liquid-repellent properties.

[0086] The amine-modified form of the present invention exhibits excellent dispersibility in liquid media, and the performance of the dispersant of the present invention is stable. Dispersants using polymeric compounds as active ingredients tend to have a wide molecular weight distribution and contain a high proportion of impurities. On the other hand, the amine-modified form allows for lower molecular weight distribution, narrowing the molecular weight distribution (simplification), and improving performance.

[0087] [Structure, etc.] The molecular weight of the amine modifier can be above 200, above 300, above 350, above 400, above 500, above 550, or above 750, and can be below 3000, below 2500, below 2000, below 1500, below 1000, below 900, below 800, below 750, or below 500.

[0088] The amine-modified forms of the present invention may not have groups containing active hydrogen. Examples of groups containing active hydrogen include amino groups (amino groups not adjacent to carbonyl groups, such as primary or secondary amino groups), hydroxyl groups, and carboxyl groups. In particular, the amine-modified forms of the present invention may not have primary or secondary amino groups not adjacent to carbonyl groups.

[0089] The amine-modified body of the present invention can be a polyamide having multiple amide structures, for example, it can be an amine (raw material amine compound, such as a polyamine) modified with multiple modifying groups (e.g., Z described below) through the amide structure. N Polyamides. Here, the amide can be an amide structure containing urethane, urea, imide, etc.

[0090] Amine-modified compounds can be compounds formed by modifying amines (raw amine compounds) with monovalent hydrocarbon groups having 6 to 40 carbon atoms.

[0091] In the amine-modified form, one or more amino groups of the amine are replaced by modifying groups. The modifying groups are preferably monovalent hydrocarbon groups that can have substituents. From the viewpoint of improving liquid repellency, the amine-modified form can be a structure in which an aliphatic hydrocarbon group with 6 to 40 carbon atoms is modified onto the amine.

[0092] Details regarding monovalent hydrocarbon groups that may have substituents follow the explanation above (monovalent hydrocarbon groups that may have substituents).

[0093] (amine skeleton) The amine-modified body of the present invention has an amine skeleton. The amine skeleton has one or more amino groups having a predetermined number of valence bonds (valences) obtained by removing a predetermined number of atoms or groups of atoms (e.g., hydrogen) from an amine compound. The amino group in the amine skeleton refers to a group selected from -NH₂, -NH⁻, and -N(-)₂, and also includes amino groups adjacent to carbonyl groups contained in amide groups, urethane groups, urea groups, imides, etc. The amine skeleton can be an aliphatic or aromatic group having one or more amino groups, but the presence of heteroatoms other than nitrogen is not excluded.

[0094] The molecular weight of the amine skeleton can be above 30, above 50, above 100, above 200, above 300, above 400 or above 500, and can be below 2800, below 2500, below 2000, below 1500, below 1000, below 750, below 600, below 450, below 300 or below 250.

[0095] The number of carbon atoms in the amine skeleton can 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 can be less than 100, less than 80, less than 60, less than 40, less than 30, less than 20, less than 10, or less than 5, preferably less than 50, and especially less than 30.

[0096] The amine skeleton has one or more amino groups. The amino groups are 1 to 3 valent amino groups, and are selected from one or more of -NH2, -NH- and -N(-)2. The number of amino groups in the amine skeleton can be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, preferably 2 or more; and can be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1.

[0097] The amine skeleton has a hydrocarbon group (aliphatic or aromatic). The hydrocarbon group can be cyclic, branched, or linear. The hydrocarbon group can be saturated or unsaturated (e.g., saturated). Here, the hydrocarbon group can be separated by oxygen and / or sulfur atoms, or it can consist only of carbon, nitrogen, and hydrogen atoms. The hydrocarbon group can be a hydrocarbon group separated by oxygen and / or sulfur atoms (e.g., a chain-like saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 aromatic hydrocarbon rings), or it can be a general hydrocarbon group (e.g., a chain-like saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 aromatic hydrocarbon rings). When the hydrocarbon group is separated by oxygen and / or sulfur atoms, it has an ether, thioether, polyether, or polysulfide structure. The number of hydrocarbon groups in the amine skeleton can be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, and can be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1.

[0098] The amine skeleton can be composed of 1- to 3-valent amino groups, and chain-like saturated aliphatic or aromatic hydrocarbon groups that can be separated by oxygen atoms and / or sulfur atoms.

[0099] The molar ratio (C / N ratio) of carbon atoms to nitrogen atoms in the amine skeleton can be 1 or more, 2 or more, 2.5 or more, 3 or more, 3.5 or more, or 4 or more; and can be 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3.5 or less, 3 or less, 2.5 or less, or 2 or less, preferably 6 or less or 4 or less.

[0100] (-Y) N -Z N n ) The amine-modified form of the present invention has one or more of the following formula: -Y N -Z N n The groups shown, [In the formula,] Y N For groups that are directly bonded or have a 1+n valence, Z N It can be a hydrocarbon group with 6 to 40 carbon atoms that has a monovalent charge and can have substituents. n is an integer greater than 1 and less than 3. There can be at least one -Y N -Z N n It bonds with the nitrogen atoms in the aforementioned amine skeleton.

[0101] The -Y of the amine-modified form N -Z N n The number can be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, preferably 2 or more; and can also be less than 12, less than 10, less than 8, less than 6, less than 4, less than 3, less than 2, or 1.

[0102] At least one -Y in the amine modifier N -Z N n It bonds to the nitrogen atoms in the amine skeleton. In the amine-modified form, all -Y atoms are present. N -Z N n In the number, the -Y atoms bonded to the nitrogen atoms of the amine skeleton N -Z N n The percentage can be 10% or more, 30% or more, 60% or more, 80% or more, or 100%, and can also be less than 100%, less than 95%, less than 75%, less than 50%, or less than 25%. -Y atoms that are not bonded to the nitrogen atoms in the amine skeleton.N -Z N n It can also bond with other groups (such as hydrocarbon groups) present in the amine skeleton.

[0103] (Y) N ) Y N It can be a directly bonded group or a group with a 1+n valence, preferably a group with a 1+n valence. N It serves to connect the amine skeleton with n Z groups N The role of the connecting base.

[0104] n is related to Y N Bonded Z N The number of elements can be an integer between 1 and 3. n can be 1 or more, 2 or more, or 3 or more, and can also be less than 3, less than 2, or less than 1, for example, less than 2.

[0105] Y N It can be an aliphatic group (unsaturated aliphatic group or saturated aliphatic group) or an aromatic group.

[0106] Y N The molecular weight can be above 10, above 50, above 100, above 200, above 300, above 500 or above 750, and can be below 2000, below 1500, below 1000, below 750, below 500 or below 300.

[0107] Y N It can have a carbonyl group. Y N It may have one or more groups selected from amide, urea, urethane, and imide, or Y N It can form one or more groups selected from amide, urea, urethane, and imide together with the amino group in the amine skeleton. Examples of such amide, urea, urethane, and imide groups can be listed as follows: -O-C(=O)-NR'-、 -NR'-C(=O)-、 -NR'-C(=O)-O-、 -NR'-C(=O)-NR'- -C(=O)-NR'- -C(=O)-NR'-C(=O)-.

[0108] [In the formula, R' is a hydrocarbon group with 1 to 30 hydrogen atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).] Y N Preferably, the nitrogen atom in the amine skeleton is bonded to the -(C=O)- group.

[0109] Y N It can be a 1+n valence group composed of one or more of the following: directly bonded, consisting of an aliphatic hydrocarbon group with 1 to 20 carbon atoms selected from -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2, -N(-)2, 2 to 4 valence aliphatic hydrocarbon rings with 1 to 20 carbon atoms, 2 to 4 valence aromatic hydrocarbon rings, and 2 to 4 valence heterocycles [where R' is a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms)].

[0110] Y N The reason for selecting Y N1 and Y N2 One or more of the following groups constitute a 1+n valence group: Y N1 It is a directly bonded group composed of one or more groups selected from -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2 and -N(-)2 (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10 or 1 to 4 carbon atoms) in each occurrence). Y N2 It is a group composed of one or more aliphatic hydrocarbon groups with 1 to 20 carbon atoms selected from 2 to 4 valence, aromatic hydrocarbon rings with 2 to 4 valence, and heterocycles with 2 to 4 valence. It can be a 1+n valence group composed of one or more groups selected from the above groups. In this specification, it is denoted as Y. N The left side of the group is bonded to the amine skeleton, and the right side is bonded to Z. N Bonding.

[0111] 〇Y N1 Y N1 It is a non-hydrocarbon linker.

[0112] Y N1 It is a directly bonded group or a group with a divalent or higher valence. Y N1 The valence can be 2–4, 2–3, or 2. Y is preferred. N1 It is not only a direct bond.

[0113] Y N1 The molecular weight can be above 10, above 50, above 100, above 200, above 300 or above 500, and can be below 2000, below 1500, below 1000, below 750 or below 500.

[0114] YN1 It can be composed of one or more groups selected from direct bonding, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2 and -N(-)2 (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10 or 1 to 4 carbon atoms) each time it appears). As Y N1 Examples can be listed as follows: direct bond, -O-、 -O-C(=O)-、 -O-C(=O)-O-、 -O-C(=O)-NR'-、 -NR'-、 -NR'-C(=O)-、 -NR'-C(=O)-O-、 -NR'-C(=O)-NR'-、 -C(=O)-、 -C(=O)-O-、 -C(=O)-NR'-、 -C(=O)-NR'-C(=O)-, -C(=NR')-、 -S-、 -SO2-, -SO2NR'-, -C(OR')R'-, -C(OR')(-)2、 -N(-)2 etc.

[0115] [In the formula, R' is independently a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) each time it appears.] Among them, in Y N1 When bonded to a nitrogen atom in the amine skeleton, the nitrogen atom can be considered as part of the amine skeleton (amino group).

[0116] 〇Y N2 Y N2 It is a linker group that can have substituents, aromatic hydrocarbon rings that can have substituents, or heterocyclic rings that can have substituents.

[0117] Y N2 It can be a hydrocarbon group or a non-hydrocarbon group (containing heteroatoms). Y N2 It can be aliphatic or aromatic. N2It can be linear, branched, or cyclic.

[0118] Y N2 It is a divalent or higher group. Y N2 The valence can be, for example, 2-4, 2-3, or 2.

[0119] Y N2 The number of carbon atoms can 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 can be less than 40, less than 35, less than 30, less than 25, less than 20, less than 15, less than 10, or less than 5.

[0120] Y N2 It is composed of one or more aliphatic hydrocarbon groups with 1 to 40 carbon atoms that may have substituents, aromatic hydrocarbon rings with 2 to 4 valences that may have substituents, and heterocycles with 2 to 4 valences that may have substituents.

[0121] Aliphatic hydrocarbon groups with 1 to 40 carbon atoms and a valence of 2 to 4 can be cyclic, branched, or straight-chain hydrocarbon groups. These groups can be saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon groups. The number of carbon atoms in these groups can be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more, and can be less than 35, less than 30, less than 25, less than 20, less than 15, less than 10, or less than 5. The valence of the aliphatic hydrocarbon group can be 2 or more, 3 or more, or 4, and can be less than 4, less than 3, or 2.

[0122] Aliphatic hydrocarbon groups may have substituents. Examples of substituents include -OR', -N(R')2, -COOR', and halogen atoms (where R' is a hydrocarbon group with 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms each time it appears). Substituents may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In aliphatic hydrocarbon groups with substituents, the amount of carbon atoms 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, relative to the amount of carbon atoms and heteroatoms; and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0123] Examples of aromatic hydrocarbon rings with 2 to 4 valences include groups formed by removing 2 to 4 hydrogen atoms from aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, benzo[a]tetraphenyl (naphthene), pentabenzene, pyrene, and phenanthrene. The number of ring atoms in the aromatic hydrocarbon ring is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valence of the aromatic hydrocarbon ring can be 2 or more, 3 or more, or 4, and can be 4 or less, 3 or less, or 2.

[0124] Aromatic hydrocarbon rings may have substituents. Examples of substituents include -R', -OR', -N(R')2, -COOR', and halogen atoms (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms each time it appears). Substituents may or may not have active hydrogen atoms. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In aromatic hydrocarbon rings with substituents, the amount of carbon atoms 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, relative to the amount of carbon atoms and heteroatoms; and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0125] The 2- to 4-valent heterocycle can be an aliphatic or aromatic group. Examples of 2- to 4-valent heterocycles include groups from pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cyclophosphine, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benziisothiazole, pyrrolidine, piperidine, piperazine, imidazole, thiazoline, etc., which have had 2 to 4 hydrogen atoms removed. The number of cyclic atoms in the heterocycle is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valence of the heterocycle can be 2 or more, 3 or more, or 4, and can be 4 or less, 3 or less, or 2.

[0126] Heterocyclic rings may have substituents. Examples of substituents include -R', -OR', -N(R')2, -COOR', and halogen atoms (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms each time it appears). Substituents may or may not have active hydrogen atoms. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In heterocyclic rings with substituents, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, for example, 65 mol% or more; and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less.

[0127] As Y N2 Examples can be listed as follows: -Ali- -Cy- -Ali (-)2 -Cy(-)2 (-)2Ali- (-)2Cy- (-)2Ali (-)2 (-)2Cy(-)2 -Ali-Cy- -Cy-Ali- -Cy-Ali-Cy- -Ali-Cy-Ali- etc.

[0128] [In the formula, Ali is an aliphatic hydrocarbon group with 1 to 20 carbon atoms, and Cy is an aromatic hydrocarbon ring or heterocycle.] As Y N2 Specific examples can be listed as follows: - (CH2) p - (p is 1-40, 1-20, or 1-10) A straight-chain hydrocarbon group with unsaturated bonds, having 1–40, 1–20, or 1–10 carbon atoms. Hydrocarbon groups with branched structures having 1–40, 1–20, or 1–10 carbon atoms - (CH2) q -Cy- (CH2) r - (q and r are independently 0 to 20, for example 1 to 10, and Cy is an aromatic hydrocarbon ring or a heterocyclic ring) etc.

[0129] ·Y N Examples For Y N Examples will be used to illustrate this. In the following text, R' is independently a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) each time it appears.

[0130] As Y N For example, in Y N When it is divalent, we can list -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 -wait.

[0131] As Y N For example, in Y N When it is trivalent, the following can be listed: -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 -Y N1 -)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 -)2 etc.

[0132] As an example of Y N when Y N is tetravalent, the following can be listed: -Y N1 (-)3、-Y N1 -Y N2 (-)3、-Y N1 -(Y N2 -)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 -(YN2 - ) 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.

[0133] As Y N For the preferred examples of, - Y can be listed 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 - YN1 (-)2 etc. In the amine-modified form, one or more Y N Preferably, the amine skeleton side end is -(C=O)- and is bonded to the nitrogen atom on the amine skeleton.

[0134] Y N Preferred is -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 shows the group.

[0135] [In the formula,] Y N1 It is independent each time it appears: direct bond, -O-、 -O-C(=O)-、 -O-C(=O)-O-、 -O-C(=O)-NR'-、 -NR'-、 -NR'-C(=O)-、 -NR'-C(=O)-O-、 -NR'-C(=O)-NR'-、 -C(=O)-、 -C(=O)-O-, or -C(=O)-NR'- -C(=O)-NR'-C(=O)-, (In the formula, R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) each time it appears.) Y N2 It is an aliphatic hydrocarbon group with 1 to 10 carbon atoms and a 2 to 4 valence, or a divalent aromatic group (e.g., a divalent phenyl group or a divalent triazole group). This allows the substrate to be endowed with good liquid repellency.

[0136] As Y N Further specific examples can be listed *-(C=O)- -O- (C=O)-NR'- etc.

[0137] [In the formula, * indicates bonding with the nitrogen atom of the amine skeleton,] R' is a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms). (Z) N ) Z N For a hydrocarbon group that can have a monovalent carbon number of 6 to 40 and may have substituents, the explanation in the above (hydrocarbon groups that can have substituents) is followed.

[0138] [Examples of amine-modified forms] (Amine modification example 1) As an example of an amine-modified form, the following formula can be cited: N(-Y N -Z N n ) p (-H) q -L 1 -[N(-Y N -Z N n ) r (-H) s -L 1 -] t -N(-Y N -Z N n ) p (-H) q The compound shown is an amine-modified example 1.

[0139] [In the formula,] Y N Each time it appears, it is independently either a directly bonded group or a group with a 1+n valence. Z N Each time it appears, it is independently a straight-chain or branched monovalent hydrocarbon group with 6 to 40 carbon atoms that can have substituents. L 1 Each time it appears, it is independently a divalent aliphatic or aromatic hydrocarbon group with 2 to 20 carbon atoms that can be separated by oxygen and / or sulfur atoms. Each time n appears, it is an integer between 1 and 3. p is an integer between 0 and 2, which is independent of p in each occurrence. Each occurrence of q is an integer between 0 and 2. p + q in each N(-Y) N -Z Nn ) p (-H) q The middle is 2. r is independently 0 or 1 each time it appears. s is independently 0 or 1 each time it appears. r+s in each N(-Y) N -Z N n ) r (-H) s The middle value is 1. The sum of all p and all r is greater than 1. t is an integer greater than 0 and less than 10. In amine modification example 1, regarding Y N Z N For details regarding n, please refer to the explanation above.

[0140] In amine-modified example 1, L 1 It is a divalent aliphatic or aromatic hydrocarbon group with 2 to 20 carbon atoms that can be separated by oxygen and / or sulfur atoms. It can be cyclic, branched, or linear, preferably a chain-like or aromatic hydrocarbon group. As L 1 The hydrocarbon group described above in the [amine skeleton] description can be used. The hydrocarbon group can be separated by oxygen atoms and / or sulfur atoms, or it can be composed of only carbon atoms, nitrogen atoms, and hydrogen atoms. L 1 For example, it can also be an aliphatic hydrocarbon group with saturated or unsaturated (e.g., saturated) or an aromatic hydrocarbon group with 1 to 2 aromatic hydrocarbon rings. 1 Preferably, it is a cyclic group that simultaneously has a ring (e.g., an aromatic ring) and a chain structure (e.g., a straight chain structure, an ether oxygen, a thioether sulfur). Specific examples include 1,3-phenylene diene, 1,4-phenylene diene, diphenyl ether diene, diphenyl thioether diene, etc. 1 The number of carbon atoms can be 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more, and can be less than 20, less than 18, less than 16, less than 14, less than 12, less than 10, less than 8, less than 6, less than 4, or less than 3.

[0141] In amine modification example 1, p is an integer greater than or equal to 0 and less than 2 each time it appears, q is an integer greater than or equal to 0 and less than 2 each time it appears, and p + q in each N(-Y N -Z N n ) p (-H) q The value of p is 2. It is preferable that p is independently greater than or equal to 1 each time it occurs, for example, 2.

[0142] In amine-modified example 1, r is independently 0 or 1 each time it appears, s is independently 0 or 1 each time it appears, and r + s in each N(-Y) N -Z N n ) r (-H) s The value of p is 1. It is preferable that p can be independently greater than 1 each time it appears, for example, 2.

[0143] The sum of all p and all r is 1 or more, that is, amine-modified example 1 has more than one -Y. N -Z N n The sum of all p and all r can be 1 or more, 3 or more, 5 or more, 7 or more, 9 or more, or 12 or more (the sum of all q and all s can also be 0), and can be less than 14, less than 12, less than 10, less than 8, less than 6, or less than 4.

[0144] In amine modification example 1, t is an integer from 0 to 10. t can be 0 or more, 1 or more, 2 or more, 4 or more, or 6 or more, preferably 0 or more or 2 or more; and t can be 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1 or less, for example, 0 or 1.

[0145] (Amine modification example 2) Other examples of amine modifiers include the following formula: N(-Y N -Z N n ) p (-H) q -L 2 (-Y N -Z N n ) u The compound shown is an amine-modified example 2.

[0146] [In the formula,] Y N Each time it appears, it is independently either a directly bonded group or a group with a 1+n valence. Z N Each time it appears, it is independently a straight-chain or branched monovalent hydrocarbon group with 6 to 40 carbon atoms that can have substituents. L 2 It is an aliphatic or aromatic hydrocarbon group with 2 to 20 carbon atoms and a +u valence that can be separated by oxygen and / or sulfur atoms. Each time n appears, it is an integer between 1 and 3. p is an integer greater than 0 and less than 2. q is an integer greater than 0 and less than 2. p + q = 2 u is an integer greater than 1 and less than 3. The sum of p and u is 1 or more. In amine modification example 2, regarding Y N Z N For details regarding n, please refer to the explanation above.

[0147] In amine-modified example 2, L 2 It is an aliphatic or aromatic hydrocarbon group with 2 to 20 carbon atoms and a +u valence that can be separated by oxygen and / or sulfur atoms. It can be a cyclic, branched, or linear hydrocarbon group, preferably a chain hydrocarbon group or an aromatic hydrocarbon group. As L 2 The hydrocarbon group described above in the [amine skeleton] description can be used. The hydrocarbon group can be separated by oxygen atoms and / or sulfur atoms, or it can be composed of only carbon atoms, nitrogen atoms, and hydrogen atoms. L 2 For example, it can also be an aliphatic hydrocarbon group with saturated or unsaturated (e.g., saturated) or an aromatic hydrocarbon group with 1 to 2 aromatic hydrocarbon rings. 2 Preferably, it is a cyclic group that simultaneously has a ring (e.g., an aromatic ring) and a chain structure (e.g., a straight chain structure, an ether oxygen, a thioether sulfur). Specific examples include 1,3-phenylene diene, 1,4-phenylene diene, diphenyl ether diene, diphenyl thioether diene, etc. 2 The number of carbon atoms can be 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more, and can be less than 20, less than 18, less than 16, less than 14, less than 12, less than 10, less than 8, less than 6, less than 4, or less than 3.

[0148] In amine modification example 2, p is an integer greater than or equal to 0 and less than or equal to 2, q is an integer greater than or equal to 0 and less than or equal to 2, and p + q equals 2. Preferably, p is 1 or more, for example, 2.

[0149] In amine modification example 2, u is an integer greater than or equal to 1 and less than or equal to 3. u is 1, 2, or 3, for example, 2 or 3.

[0150] In amine-modified embodiment 2, the sum of p and u is 1 or more, that is, amine-modified embodiment 2 has one or more -Y N -Z N n The total of all p and u can be 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more (the total of all q can also be 0), and the total of p and u can be less than 5, less than 4, less than 3, or less than 2.

[0151] (Specific example) Specific examples of amine-modified compounds include compounds represented by the following formulas. In the following formulas, details regarding Z follow the same pattern as described above.N . Amine modifiers can be synthetic waxes derived from animal or vegetable oils. Synthetic waxes are obtained by condensing fatty acids from animal or vegetable oils with aliphatic or aromatic amines. Examples of synthetic waxes include fatty acid amide compounds such as hydroxy fatty acid amides, palmitamides, octadecanoic acid amides, stearamides, eicosanoic acid amides, betaine compounds, tetracosanoic acid amides, oleamides, linoleamides, α-linolenic acid amides, γ-linolenic acid amides, eicosapentaenoic acid amides, and docosahexaenoic acid amides.

[0152] [Manufacturing Method] There are no limitations on the manufacturing method of the amine modifier; examples include: making a Z-containing... N A method for synthesizing Z-containing carboxylic acids by reacting them with various amines (starting amines) in the presence of a desired condensing agent; N Methods for synthesizing amines include the reaction of acyl chlorides, anhydrides, isocyanates, etc., of carboxylic acids with various amines (starting amines). The condensing agent can be a well-known condensing agent, such as DCC, EDCI, CDI, BOP, COMU, DMT-MM, DPPA, Py-Bop, etc.

[0153] (Amine (raw material amine)) Examples of amines (raw material amines) that serve as precursors to the amine skeleton include amines capable of forming the amine skeleton, such as: alkylamines like methylamine, ethylamine, propylamine, butylamine, and dibutylamine; alkylene diamines like ethylenediamine, propylenediamine, butylamine, pentanediamine, hexamethylenediamine, cyclohexanediamine, and methylenedicyclohexylamine; and diethylenetriamine, triethylenetetramine, tri(2-aminoethyl)amine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tri(2-aminopropyl)amine, tetrapropylenepentamine, pentapropylenehexamine, iminodipropylamine, dibutyltriamine, bis(2-aminoethoxy)ethane, bis(2-aminoethyl) ether, and bis[2-(2-aminoethoxy)]ethane. Polyalkylene polyamines such as ethyl ether, bis[2-(3-aminopropoxy)ethyl] ether, spermine, spermidine, etc.; oxygen- or sulfur-containing aliphatic amines such as 1-aminopropanediol, 2-amino-1,3-propanediol, 3-amino-1,2-propanediol, polyoxypropylene diamine, polyoxyethylene diamine, etc.; aromatic monoamines such as aniline, 1-naphthylamine or 2-naphthylamine, 1-aminoanthracene, 2-aminoanthracene or 9-aminoanthracene, 9-aminophenanthrene, 2-aminobiphenyl, 3-aminobiphenyl or 4-aminobiphenyl, etc.; o-phenylenediamine, m-phenylenediamine or p-phenylenediamine, o-phenylenediamine, m-phenylenediamine or p-phenylenediamine, diaminotoluene, 2,3-toluenediamine, 2,4-toluenediamine or 2,5-toluenediamine. Monocyclic aromatic polyamines, etc.; diaminobiphenyl, bisaminophenoxyphenylpropane, diaminodiphenyl ether, diaminodiphenyl sulfide, diaminodiphenyl sulfone, diaminobenzophenone, diaminodiphenylmethane, diaminophenylpropane, diaminophenylhexafluoropropane, diaminophenylphenylethane, bisaminophenoxybenzene, bisaminobenzoylbenzene, bisaminodimethylbenzylbenzene, aminophenoxybiphenyl, aminophenoxyphenyl ketone, bisaminodi(trifluoromethyl)benzylbenzene, aminophenoxyphenyl sulfone, aminophenoxyphenyl ether, aminophenoxyphenylpropane, bis(aminophenoxybenzoyl)benzene, bis(aminophenoxy-α,α-dimethylbenzyl)benzene, bis[(aminoaryloxy)benzoyl]di Polycyclic aromatic polyamines including phenyl ether, bis(amino-α,α-dimethylbenzylphenoxy)benzophenone, aminophenoxyphenyl sulfide, bis[amino-α,α-dimethylbenzylphenoxy]diphenyl sulfone, 4,4'-bis[aminophenoxyphenoxy]diphenyl sulfone, diaminodiaryloxybenzophenone, diaminoaryloxybenzophenone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diaminotriphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-methylenebisphenylamine, 4,4'-oxodiphenylamine, 1,3-bis(4-aminophenoxy)benzene, 4,4'-diaminodiphenyl ether, 4,4'-bis(aminophenyl)amine, etc.Polyamines containing oxygen or sulfur, 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; and hydroxyl-containing polyamines, such as 2-hydroxyethylethylenediamine, 2-hydroxyethylpropanediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropanediamine, 2-hydroxypropylethylenediamine, and di-2-hydroxypropylethylenediamine. Polyamines can be formed by polymerizing polymerizable compounds such as allylamine.

[0154] [Polyol Modified Forms] As an example of a liquid-repellent compound, a polyol-modified compound will be described. A polyol-modified compound is a polyol compound that has been chemically modified to exhibit liquid-repellent properties.

[0155] [Structure, etc.] The polyol modifier can be a polymer with a degree of polymerization of 1 or higher. From the viewpoint of improving liquid repellency, the degree of polymerization of the polyol modifier can be 2 or higher, 3 or higher, 5 or higher, 6 or higher, preferably 7 or higher, more preferably 8 or higher, and even more preferably 9 or higher; from the viewpoint of improving the operability of the repellent, it can be 100 or lower, preferably 50 or lower, more preferably 30 or lower, and even more preferably 15 or lower. Here, the degree of polymerization refers to the number of repetitions of the monomer units constituting the polymer.

[0156] In this invention, the degree of polymerization refers to the average degree of polymerization. The average degree of polymerization in this invention refers to the degree of polymerization measured under the following conditions.

[0157] In the case where the polyol modified body of the present invention is a polyglycerol modified body obtained by modifying polyglycerol, the degree of polymerization of the polyol modified body refers to the average degree of polymerization of the polyglycerol. The average degree of polymerization of polyglycerol is the average degree of polymerization (n) calculated from the hydroxyl value using end-group analysis. Specifically, the average degree of polymerization and the average molecular weight are calculated using the following formulas (Formula 1) and (Formula 2).

[0158] (Equation 1) Average molecular weight = 74n + 18; (Equation 2) Hydroxyl value = 56110(n+2) / average molecular weight.

[0159] The hydroxyl value in Equation 2 above is a numerical value indicating the number of hydroxyl groups in polyglycerol. The hydroxyl value is calculated based on the amount of potassium hydroxide required to neutralize the acetic acid needed to acetylate 1g of free hydroxyl groups in polyglycerol. This can be calculated according to the "Standard Oil Analysis Test Method (I), 2003 Edition" compiled by the Japan Oil Chemical Society. The hydroxyl value of the polyglycerol used as raw material can be measured according to the aforementioned Standard Oil Analysis Test Method, and then the average degree of polymerization and average molecular weight of the polyglycerol can be calculated using the above formula.

[0160] In the case where the polyol modified body of the present invention is a polyvinyl alcohol modified body obtained by modifying polyvinyl alcohol, the degree of polymerization of the polyol modified body refers to the average degree of polymerization of the polyvinyl alcohol. The average degree of polymerization of polyvinyl alcohol can be determined according to JIS K 6726, the test method for polyvinyl alcohol.

[0161] In the case where the polyol modifier of the present invention is a polysaccharide modifier obtained by modifying polysaccharides, the degree of polymerization of the polyol modifier refers to the average degree of polymerization of the aforementioned polysaccharides. The analysis of the average degree of polymerization of the polysaccharides can be performed as follows. The degree of polymerization refers to the number of monosaccharide units (fructose and glucose units) in the polysaccharide. The average degree of polymerization can be, for example, the peak value among the peaks of each analytical result obtained by conventional analytical methods such as HPLC, GC, and HPAEC as described below. As a chromatographic column, for example, a ULTRON PS-80N (8×300mm) (solvent: water, flow rate: 0.5ml / min, temperature: 50°C) manufactured by Shin-Ho Chemical or a TSK-GEL G30000 PWXL (7.8×300mm) manufactured by TOSOH (solvent: water, flow rate: 0.5ml / min, temperature: 50°C) can be used. As a detector, a differential refractometer can be used for measurement.

[0162] The polyol modifier can be a low molecular weight (e.g., a weight-average molecular weight of less than 1500, less than 1000, or less than 500) and / or a high molecular weight. The weight-average molecular weight of the polyol modifier can be above 100, above 200, above 300, above 400, above 500, above 1000, above 3000, above 5000, above 10000, above 30000, above 100000, above 300000, above 300000, or above 500000. It can also be below 1,000,000, below 750,000, below 500,000, below 300,000, below 100,000, below 75,000, below 50,000, below 30,000, below 10,000, below 9,000, below 8,000, below 7,000, below 6,000, below 5,000, below 3,000, below 2,000, below 1,000, or below 500.

[0163] The substitution rate of the hydroxyl groups in the polyol modifier can 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 can be less than 100%, less than 95%, less than 85%, less than 75%, less than 65%, less than 55%, less than 45%, less than 35%, less than 25%, less than 15%, for example, less than 95%. Here, "substitution rate" refers to the proportion (mol%) of the hydroxyl groups from the polyol source that are modified, meaning the proportion (mol%) modified by a hydrocarbon group with 6 or more to 40 monovalent carbon atoms that can have substituents.

[0164] The residual percentage of hydroxyl groups in the polyol modifier can 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 can also be less than 100%, less than 95%, less than 85%, less than 75%, less than 65%, less than 55%, less than 45%, less than 35%, less than 25%, less than 15%, or less than 5%, for example, less than 50%, less than 30%, or less than 10%. Here, "residual percentage" refers to the proportion (mol%) of unmodified hydroxyl groups from the polyol source.

[0165] The number of modifying groups in the polyol modifier can 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 can be less than 1000, less than 750, less than 500, less than 300, less than 100, less than 50, less than 30, or less than 20. Preferably, the modifying group is a monovalent hydrocarbon group that can have substituents.

[0166] The equivalent of the modifying group in the polyol modifier can 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 can be less than 2500, less than 2000, less than 1500, less than 1000, less than 750, less than 500, or less than 400, which is the value obtained by dividing the weight-average molecular weight of the polyol modifier by the number of modifying groups. Here, the modifying group is preferably a monovalent hydrocarbon group that can have substituents.

[0167] In the polyol modifier, one or more hydroxyl groups of the polyol are replaced by a modifying group. The modifying group is preferably a monovalent hydrocarbon group that can have a substituent. From the viewpoint of improving liquid repellency, the polyol modifier can be a structure in which an aliphatic hydrocarbon group with 6 to 40 carbon atoms is modified onto the polyol.

[0168] For details regarding monovalent hydrocarbon groups that may have substituents, the above description of (monovalent hydrocarbon groups that may have substituents) is used.

[0169] (-Y) O -Z O n ) In the polyol modifier of the present invention, one or more hydroxyl groups of the polyol can be expressed by the following formula: -Y O -Z O n The groups shown are substituted.

[0170] [In the formula,] Y O The reason for selecting Y O1 and Y O2 One or more of the following groups constitute a 1+n valence group: Y O1 It is a directly bonded group composed of one or more groups selected from -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2 and -N(-)2 (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10 or 1 to 4 carbon atoms) in each occurrence). Y O2 It is a group composed of one or more aliphatic hydrocarbon groups with 1 to 40 carbon atoms that may have substituents, aromatic hydrocarbon rings with 2 to 4 valences that may have substituents, and heterocycles with 2 to 4 valences that may have substituents. Z O It can be a hydrocarbon group with 6 to 40 carbon atoms that has a monovalent charge and can have substituents. n is an integer greater than 1 and less than 3. (Y) O ) Y O The reason for selecting Y O1 and Y O2 One or more of the following groups constitute a 1+n valence group: Y O1It is a directly bonded group composed of one or more groups selected from -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2 and -N(-)2 (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10 or 1 to 4 carbon atoms) in each occurrence). Y O2 It is a group composed of one or more of an aliphatic hydrocarbon group with 1 to 40 carbon atoms that may have substituents, an aromatic hydrocarbon ring with 2 to 4 valences that may have substituents, and a heterocycle with 2 to 4 valences that may have substituents.

[0171] n is related to Y O Bonded Z O The number of elements can be an integer between 1 and 3. n can be 1 or more, 2 or more, or 3 or more, and can also be less than 3, less than 2, or less than 1, for example, less than 2.

[0172] Y O The molecular weight can be above 10, above 50, above 100, above 200, above 300, above 500, or above 750, and can be below 3000, below 2500, below 2000, below 1500, below 1000, below 750, below 500, below 300, below 200, below 100, or below 50.

[0173] Y O It may contain at least an amide group, an amino ester group, a urea group, an imide group, a thioamide group, a thioamino ester group, a thiourea group, a thioimide group, a sulfonamide group, a sulfonylurea group, a sulfonamide group, or a sulfonamide group. For example, Y O It can contain -C(=O)-NR'-, -C(=S)-NR'-, -O-C(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'-, or -SO2NR'-. Through Y O The presence of these groups improves liquid repellency.

[0174] ○ Y O1 Y O1 It is a non-hydrocarbon linker.

[0175] Y O1 It is a directly bonded group or a group with a divalent or higher valence. Y O1 The valence can be 2–4, 2–3, or 2. Y is preferred. O1 It is not only a direct bond.

[0176] Y O1The molecular weight can be above 10, above 50, above 100, above 200, above 300 or above 500, and can be below 2000, below 1500, below 1000, below 750 or below 500.

[0177] Y O1 It is composed of one or more groups selected from direct bonding, -O-, -C(=O)-, -S(=O)2-, -NR'-, -C(OR')R'-, and -C(OR')(-)2 (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) each time it appears). As Y O1 Examples can be listed as follows: direct bond, -O-、 -O-C (=O)-, -O-C (=O)-O-, -O-C (=O)-NR'-, -NR'-、 -NR'-C(=O)-、 -NR'-C(=O)-O-, -NR'-C (=O)-NR'-, -C (=O)-, -C (=O) -O-, -C(=O)-NR'-, -SO2-, -SO2NR'-, -C(OR')R'-, -C(OR')(-)2 etc.

[0178] (In the formula, R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) each time it appears.) Y O1 It may contain at least an amide group, an amino ester group, a urea group, an imide group, a thioamide group, a thioamino ester group, a thiourea group, a thioimide group, a sulfonamide group, a sulfonylurea group, a sulfonamide group, or a sulfonamide group. For example, Y O2 It can contain -C(=O)-NR'-, -O-C(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'-, or -SO2NR'-. Through Y O1 The presence of these groups improves liquid repellency.

[0179] ○ Y O2 Y O2It is a linker group that can have substituents, aromatic hydrocarbon rings that can have substituents, or heterocyclic rings that can have substituents.

[0180] Y O2 It can be a hydrocarbon group or a non-hydrocarbon group (containing heteroatoms). Y O2 It can be aliphatic or aromatic. O2 It can be linear, branched, or cyclic.

[0181] Y O2 It is a divalent or higher group. Y O2 The valence can be, for example, 2-4, 2-3, or 2.

[0182] Y O2 The number of carbon atoms can 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 can be less than 40, less than 35, less than 30, less than 25, less than 20, less than 15, less than 10, or less than 5.

[0183] Y O2 It is composed of one or more aliphatic hydrocarbon groups with 1 to 40 carbon atoms that may have substituents, aromatic hydrocarbon rings with 2 to 4 valences that may have substituents, and heterocycles with 2 to 4 valences that may have substituents.

[0184] Aliphatic hydrocarbon groups with 1 to 40 carbon atoms and a valence of 2 to 4 can be cyclic, branched, or straight-chain hydrocarbon groups. These groups can be saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon groups. The number of carbon atoms in these groups can be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more, and can be less than 35, less than 30, less than 25, less than 20, less than 15, less than 10, or less than 5. The valence of the aliphatic hydrocarbon group can be 2 or more, 3 or more, or 4, and can be less than 4, less than 3, or 2.

[0185] Aliphatic hydrocarbon groups may have substituents. Examples of substituents include -OR', -N(R')2, -COOR', and halogen atoms (where R' is independently a hydrocarbon group with 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms each time it appears). Substituents may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In aliphatic hydrocarbon groups with substituents, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0186] Examples of aromatic hydrocarbon rings with 2 to 4 valences include groups formed by removing 2 to 4 hydrogen atoms from aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, benzo[a]tetraphenyl (naphthene), pentabenzene, pyrene, and phenanthrene. The number of ring atoms in the aromatic hydrocarbon ring is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valence of the aromatic hydrocarbon ring can be 2 or more, 3 or more, or 4, and can be 4 or less, 3 or less, or 2.

[0187] Aromatic hydrocarbon rings may have substituents. Examples of substituents include -R', -OR', -N(R')2, -COOR', and halogen atoms (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms each time it appears). Substituents may or may not have active hydrogen atoms. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In aromatic hydrocarbon rings with substituents, the amount of carbon atoms 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, relative to the amount of carbon atoms and heteroatoms; and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0188] The 2- to 4-valent heterocycle can be an aliphatic or aromatic group. Examples of 2- to 4-valent heterocycles include groups from pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cyclophosphine, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benziisothiazole, pyrrolidine, piperidine, piperazine, imidazole, thiazoline, etc., which have had 2 to 4 hydrogen atoms removed. The number of cyclic atoms in the heterocycle is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valence of the heterocycle can be 2 or more, 3 or more, or 4, and can be 4 or less, 3 or less, or 2.

[0189] Heterocyclic rings may have substituents. Examples of substituents include -R', -OR', -N(R')2, -COOR', and halogen atoms (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms each time it appears). Substituents may or may not have active hydrogen atoms. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In heterocyclic rings with substituents, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, for example, 65 mol% or more; and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less.

[0190] As Y O2 Examples can be listed as follows: -Ali- -Cy- -Ali (-)2 -Cy(-)2 (-)2Ali- (-)2Cy- (-)2Ali (-)2 (-)2Cy(-)2 -Ali-Cy- -Cy-Ali- -Cy-Ali-Cy- -Ali-Cy-Ali- etc.

[0191] [In the formula, Ali is an aliphatic hydrocarbon group with 1 to 20 carbon atoms, and Cy is an aromatic hydrocarbon ring or heterocycle.] As Y O2 Specific examples can be listed as follows: - (CH2)p - (p is 1-40, 1-20, or 1-10) A straight-chain hydrocarbon group with unsaturated bonds, having 1–40, 1–20, or 1–10 carbon atoms. Hydrocarbon groups with branched structures having 1–40, 1–20, or 1–10 carbon atoms - (CH2) q -Cy- (CH2) r - (q and r are independently 0 to 20, for example 1 to 10, and Cy is an aromatic hydrocarbon ring or a heterocyclic ring) etc.

[0192] (Y) O (Example) For Y O Examples will be used to illustrate this. In the following text, R' is independently a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) each time it appears.

[0193] As Y O For example, in Y O When it is divalent, we can list -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 -、-Y O2 -Y O1 -Y O2 -、-Y O2 -Y O1 -Y O2 -Y O1 -wait.

[0194] As Y O For example, in Y O When it is trivalent, the following can be listed: -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 -Y O2 -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.

[0195] As Y O For example, when Y O is tetravalent, the following can be listed: -Y O1 (-) 3, -Y O1 -YO2 (-)3 -Y O1 -(AND O2 -)3 -Y O1 -AND O2 -AND O1 (-)3 -Y O1 -AND O2 (-AND O1 -)3 -Y O1 -(AND O2 -AND O1 -)3 -Y O1 -AND O2 -AND O1 -AND O2 (-)3 -Y O1 -AND O2 -AND O1 -(AND O2 -) 3、 -AND O1 -AND O2 -(AND O1 -AND O2 -) 3、 -AND O1 -(AND O2 -AND O1 -AND O2 -)3; -AND O2 (-)3 -Y O2 -AND O1 (-)3 -Y O2 -(AND O1 -)3 -Y O2 -AND O1 -AND O2 (-)3 -Y O2 -AND O1 (-AND O2 -)3 -Y O2 -(AND O1 -AND O2 -)3 -Y O2 -AND O1 -AND O2 -AND O1 (-)3 -Y O2 -AND O1 -AND O2 -(AND O1 -) 3、 -AND O2 -AND O1 -(AND O2 -AND O1 -) 3、 -AND O2 -(AND O1 -AND O2 -ANDO1 -) 3, etc.

[0196] As Y O Preferred examples can be listed as -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.

[0197] (Y) O (Preferred example) Y O -O-Y can be preferred. O11 - or -O-Y O11 -Y O21 -Y O12 -.

[0198] [In the formula, each symbol appears independently each time.] Y O11 For direct bonding, -C(=O)-, -C(=O)-NR'-, or -C(=S)-NR'-. Y O21 It consists of hydrocarbon groups with 1 to 40 carbon atoms. Y O12 are -O-, -O-C (=O)-, -O-C (=O)-O-, -C (=O)-NR'-, -O-C (=O)-NR'-, -NR'-, -NR'-C (=O)-, -NR'-C (=O)-O- , -NR'-C (=O) -NR'-, -C (=O)-, -C (=O) -O-, -C (=O) -NR'-, -SO2-, -SO2NR'-, -C (OR')R'- or -C (OR') (-)2. ] Y O11 It is a non-hydrocarbon linker, which is a directly bonded or divalent or higher group.

[0199] Y O11 The molecular weight can be above 10, above 50, above 100, above 200, above 300 or above 500, and can be below 2000, below 1500, below 1000, below 750 or below 500.

[0200] Y O11 It can be a direct bond, -C(=O)-, -C(=O)-NR'-, or -C(=S)-NR'-.

[0201] Y O21 It is a divalent hydrocarbon linker, which can be a hydrocarbon group with 1 to 40 carbon atoms.

[0202] Y O21 The number of carbon atoms can 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 can be less than 40, less than 35, less than 30, less than 25, less than 20, less than 15, less than 10, or less than 5.

[0203] Here, the hydrocarbon group with 1 to 40 carbon atoms can be a cyclic, branched, or straight-chain hydrocarbon group, and can be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group.

[0204] As Y O21 Specific examples can be listed as follows: - (CH2) p - (p is 1-40, 1-20, or 1-10) A straight-chain hydrocarbon group with unsaturated bonds, having 1–40, 1–20, or 1–10 carbon atoms. Hydrocarbon groups with branched structures having 1–40, 1–20, or 1–10 carbon atoms - (CH2) q -Cy- (CH2) r - (q and r are independently 0 to 20, for example 1 to 10, and Cy is an aromatic hydrocarbon ring or a heterocyclic ring) etc.

[0205] Y O12 Can be -O-, -O-C(=O)-, -O-C(=O)-O-, -O-C(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR' -C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO2-, -SO2NR'-, -C(OR')R'- or -C(OR')(-)2.

[0206] Y O12 It may contain at least an amide group, an amino ester group, a urea group, an imide group, a thioamide group, a thioamino ester group, a thiourea group, a thioimide group, a sulfonamide group, a sulfonylurea group, a sulfonamide group, or a sulfonamide group. For example, Y O12It can be -C(=O)-NR'-, -O-C(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'-, or -SO2NR'-. Through Y C12 The presence of these groups improves liquid repellency.

[0207] (Z) O ) Z O For a hydrocarbon group that can have a monovalent carbon number of 6 to 40 and may have substituents, the explanation in the above (hydrocarbon groups that can have substituents) is followed.

[0208] [Other modifying groups] The hydroxyl groups of polyols can be -Y O -Z O n Other modifying groups may be substituted. Examples of modifying groups include anionic and / or cationic groups.

[0209] Monomers having carboxyl, sulfonic acid, or phosphate groups can be listed as anionic groups.

[0210] Salts that are anionic groups can be alkali metal salts, alkaline earth metal salts, or ammonium salts, such as methyl ammonium salts, ethanol ammonium salts, triethanolammonium salts, etc.

[0211] As cationic groups, there are amino, preferably tertiary amine, and quaternary ammonium groups. In the tertiary amine group, the two groups bonded to the nitrogen atom may be the same or different, preferably an aliphatic group (especially alkyl) with 1 to 5 carbon atoms, an aromatic group (aryl) with 6 to 20 carbon atoms, or an aromatic aliphatic group (especially aralkyl, for example benzyl (C6H5-CH2-)) with 7 to 25 carbon atoms. In the quaternary ammonium group, the three groups bonded to the nitrogen atom may be the same or different, preferably an aliphatic group (especially alkyl) with 1 to 5 carbon atoms, an aromatic group (aryl) with 6 to 20 carbon atoms, or an aromatic aliphatic group (especially aralkyl, for example benzyl (C6H5-CH2-)) with 7 to 25 carbon atoms. In the tertiary amine and quaternary ammonium groups, 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.

[0212] The cationic group of the salt is a salt formed with an acid (organic acid or inorganic acid). Organic acids are preferred, such as carboxylic acids with 1 to 20 carbon atoms (especially monocarboxylic acids such as acetic acid, propionic acid, butyric acid, stearic acid, etc.).

[0213] [Manufacturing Method] Polyol modifiers can be manufactured by reacting a modifier having a modifying group (or a precursor structure of the modifying group) with the hydroxyl group of the polyol.

[0214] (Polyols) Polyols are compounds with two or more hydroxyl groups and are used as raw materials for polyol modifiers. A polyol is a compound with two or more hydroxyl groups within its molecule. Polyols can be aliphatic or aromatic, preferably aliphatic.

[0215] Polyols may have ether bonds. Preferably, polyols may have two or more ether bonds. Specifically, polyols are preferably compounds having two or more hydroxyl groups and two or more ether bonds. In other words, polyols are preferably polyethers having two or more hydroxyl groups.

[0216] In the case of polyols as polymers, the repeating structure of monomer units can contain hydroxyl and ether bonds.

[0217] Polyols can be low molecular weight (e.g., weight average molecular weight less than 1000, below 500) and / or high molecular weight. The weight average molecular weight of polyols can be above 50, above 100, above 300, above 500, above 1000, above 3000, above 5000, above 10000, above 30000, above 100000, above 300000, or above 500000, and can be below 1000000, below 750000, below 500000, below 300000, below 100000, below 75000, below 50000, below 30000, below 10000, below 5000, below 3000, below 2000, below 1000, or below 500.

[0218] The number of hydroxyl groups in a polyol can 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 can be less than 3000, less than 1000, less than 750, less than 500, less than 300, less than 100, less than 50, less than 30, or less than 20.

[0219] The hydroxyl equivalent of a polyol can be 20 or higher, 40 or higher, 60 or higher, 80 or higher, 100 or higher, 120 or higher, or 150 or higher, and can also be below 1000, below 800, below 600, below 400, below 200, below 100, or below 75. The hydroxyl equivalent of a polyol is the value obtained by dividing the weight-average molecular weight of the polyol by the number of hydroxyl groups.

[0220] Polyols can be natural products. These natural products can be high-molecular-weight natural products, low-molecular-weight natural products, or their derivatives. The aforementioned natural products also include compounds transformed by microorganisms. Examples of polyols include monosaccharides, oligosaccharides, polysaccharides, sugar alcohols (reducing sugars), hydroxy acids, amino acids, vitamins, flavonols, hydroxy hydrocarbons, hydroxyl-containing polymers, polyether polyols, polymer polyols, polyester polyols, and other polyols.

[0221] Examples of monosaccharides include glucose, fructose, galactose, and xylose.

[0222] Examples of oligosaccharides include sucrose, cyclic starch, cyclodextrin, maltose, trehalose, lactose, and sucralose.

[0223] Examples of sugar alcohols (reducing sugars) include sorbitol, maltitol, erythritol, isomaltitol, lactitol, mannitol, xylitol, dehydrated sorbitol, and lactitol.

[0224] Examples of polysaccharides include starch, cellulose, gel polysaccharides, pullulan, alginic acid, carrageenan, guar gum, chitin, chitosan, locust bean gum, κ-carrageenan, ι-carrageenan, isomaltulin, gellan gum, tamarind gum, etc.

[0225] Examples of hydroxy acids include ascorbic acid, kojic acid, quinic acid, chlorogenic acid, and gluconic acid.

[0226] Examples of amino acids include glucosamine, etc.

[0227] Examples of vitamins include ascorbic acid and inositol.

[0228] Examples of flavonols include catechins, quercetin, and anthocyanins.

[0229] Examples of hydroxy hydrocarbons include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, glycerol, trimethylolpropane, and trimethylolethane. Hydroxy hydrocarbons are hydrocarbons containing a hydroxyl group; they can be aromatic or aliphatic, preferably aliphatic. When referring to hydroxy hydrocarbons, it can also refer to hydroxy hydrocarbons other than those included in other groups such as polysaccharides (other hydroxy hydrocarbons).

[0230] Examples of polymers containing hydroxyl compounds include polyglycerol, polyvinyl alcohol, hydroxyethyl methacrylate polymers, hydroxypropyl methacrylate polymers, and hydroxybutyl methacrylate polymers.

[0231] Examples of polyether polyols include compounds obtained by adding olefin oxides to an initiator. Initiators can be compounds having two or more functional hydroxyl groups. Examples of initiators include propylene glycol, polypropylene glycol, ethylene glycol, polyethylene glycol, glycerol, polyglycerol, trimethylolpropane, triethanolamine, pentaerythritol, ethylenediamine, aromatic diamines, diethylenetriamine, sorbitol, and sucrose. Examples of olefin oxides include ethylene oxide and propylene oxide. Polyether polyols obtained by adding olefin oxides to the above-mentioned initiators are also called polyoxyalkylene polyols or alkylene derivatives of polyols. Representative examples of polyether polyols include polyoxypropylene triol obtained by adding propylene oxide to glycerol, and polyoxypropylene polyglycidyl ether obtained by adding propylene oxide to polyglycerol.

[0232] Examples of polymeric polyols include compounds obtained by polymerizing at least a portion of a polyether polyol with an olefinically unsaturated monomer. Examples of such olefinically unsaturated monomers include acrylonitrile and styrene.

[0233] Examples of polyester polyols include compounds obtained by dehydration condensation of compounds with two or more carboxyl groups and compounds with two or more hydroxyl groups. Examples of compounds with two or more carboxyl groups include terephthalic acid, isophthalic acid, phthalic acid, methyl phthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, succinic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, and their anhydrides. Examples of compounds with two or more hydroxyl groups include ethylene glycol, propylene glycol, propanediol, neopentyl glycol, glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, and their polymers.

[0234] (Modifier) The modifier is a compound that is reactive with polyols, preferably the above-mentioned compound containing a hydrocarbon group with 6 to 40 monovalent carbon atoms that may have substituents.

[0235] Examples of modifiers are as follows.

[0236] Acyl halide G(O=)C-Z O Acid anhydride O(C(=O)-Z) O )2 Carboxylic acid HO (O=) C-Z O Isocyanates O=C=N-Z O Thioisocyanates S=C=N-Z O Epoxy (CH2OCH)CH2O-Z O Halides G-Z O Amine H2N-Z O Hydroxyl HO-Z O [In the formula, Z] O As mentioned above, G is a halogen atom (e.g., F, Cl, Br, or I). The Z in the structure of the above-mentioned modifiers can also be... O Replace it with any group that constitutes the modifying group; for example, Z can be made O It can be a hydrocarbon group with a monovalent carbon number of 6 to 40 that can have substituents, for example, it can be a Z-type hydrocarbon group. O For -Y O -Z O n .

[0237] Polyol modifiers can be synthesized by reacting polyols with modifiers. For example, polyol modifiers can be synthesized by reacting acyl halides, acid anhydrides, or carboxylic acids as modifiers with the hydroxyl groups of polyols to form ester bonds. Alternatively, polyol modifiers can be generated by reacting halides or epoxides as modifiers with the hydroxyl groups of polyols to form ether bonds. Regarding the reaction conditions between polyols and modifiers, those skilled in the art can appropriately design the conditions using catalysts (e.g., acid catalysts, base catalysts), condensing agents, etc., depending on the target product.

[0238] [Polycarboxylic acid modified forms] As an example of a liquid-repellent compound, a polycarboxylic acid modified compound is described. A polycarboxylic acid modified compound is a compound that has been chemically modified to exhibit liquid-repellent properties.

[0239] [Structure, etc.] The polycarboxylic acid modifier can be a low molecular weight (e.g., a weight-average molecular weight of less than 1500, less than 1000, or less than 500) and / or a high molecular weight. The weight-average molecular weight of the polycarboxylic acid modifier can be above 100, above 200, above 300, above 400, above 500, above 1000, above 3000, above 5000, above 10000, above 30000, above 100000, above 300000, or above 500000. It can also be below 1,000,000, below 750,000, below 500,000, below 300,000, below 100,000, below 75,000, below 50,000, below 30,000, below 10,000, below 9,000, below 8,000, below 7,000, below 6,000, below 5,000, below 3,000, below 2,000, below 1,000, or below 500.

[0240] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polycarboxylic acid modifiers can be obtained by GFC analysis using polyethylene glycol / polyoxyethylene as a standard sample under the following apparatus and conditions.

[0241] Separation column: SB-806M (8mm×30mm, Shodex) Column temperature: 40℃ Mobile phase solvent: ion-exchanged water Mobile phase flow rate: 1.0 mL / min Sample concentration: 0.5 wt% Injection volume: 50μL Detector: RI detector (Waters2414, Waters Corporation).

[0242] The weight-average molecular weight (Mw), number-average molecular weight (Mn), and polydispersity index (Mw / Mn) of polycarboxylic acid modified polystyrene can be determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as the eluent and Shodex KF400RL and KF400RH columns (polystyrene gel) manufactured by Showa Denko Corporation.

[0243] The substitution rate of the hydroxyl group of the carboxyl group in the polycarboxylic acid modified body can 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 can be less than 100%, less than 95%, less than 85%, less than 75%, less than 65%, less than 55%, less than 45%, less than 35%, less than 25%, less than 15%, for example, less than 95%. Here, "substitution rate" refers to the proportion (mol%) of the hydroxyl group of the carboxyl group derived from the polycarboxylic acid that is modified, meaning the proportion (mol%) modified by a hydrocarbon group with 6 or more to 40 monovalent carbon atoms that can have substituents.

[0244] The residual percentage of the hydroxyl groups of the carboxyl groups in the polycarboxylic acid modified body can 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 can also be less than 100%, less than 95%, less than 85%, less than 75%, less than 65%, less than 55%, less than 45%, less than 35%, less than 25%, less than 15%, or less than 5%, for example, less than 50%, less than 30%, or less than 10%. Here, "residual percentage" refers to the proportion (mol%) of the hydroxyl groups of the carboxyl groups derived from the polycarboxylic acid that are not modified.

[0245] The number of modifying groups in the polycarboxylic acid modifier can be 2 or more, 5 or more, 7 or more, 10 or more, 15 or more, 30 or more, or 50 or more, and can be less than 1000, less than 750, less than 500, less than 300, less than 100, less than 50, less than 30, or less than 20. Preferably, the modifying group is a monovalent hydrocarbon group that can have substituents.

[0246] The equivalent of the modifying group in the polycarboxylic acid modifier can 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 can be less than 2500, less than 2000, less than 1500, less than 1000, less than 750, less than 500, or less than 400, which is the value obtained by dividing the weight-average molecular weight of the polycarboxylic acid modifier by the number of modifying groups. Here, the modifying group is preferably a monovalent hydrocarbon group that can have substituents.

[0247] In a polycarboxylic acid modifier, one or more hydroxyl groups of the polycarboxylic acid are replaced by a modifying group. The modifying group is preferably a monovalent hydrocarbon group that can have substituents. From the viewpoint of improving liquid repellency, the polycarboxylic acid modifier may have an aliphatic hydrocarbon group with 6 to 40 carbon atoms on the polycarboxylic acid.

[0248] For details regarding monovalent hydrocarbon groups that may have substituents, the above description of (monovalent hydrocarbon groups that may have substituents) is used.

[0249] (-Y) C -Z C n ) In the polycarboxylic acid modified body of the present invention, the hydroxyl groups of one or more carboxyl groups of the polycarboxylic acid can be represented by the following formula: -Y C -Z C n The groups shown are substituted.

[0250] [In the formula,] Y C The reason for selecting Y C1 and Y C2 One or more of the following groups constitute a 1+n valence group: Y C1 It is a directly bonded group composed of one or more groups selected from -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2 and -N(-)2 (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10 or 1 to 4 carbon atoms) in each occurrence). Y C2 It is a group composed of one or more aliphatic hydrocarbon groups with 1 to 40 carbon atoms that may have substituents, aromatic hydrocarbon rings with 2 to 4 valences that may have substituents, and heterocycles with 2 to 4 valences that may have substituents. Z C It can be a hydrocarbon group with 6 to 40 carbon atoms that has a monovalent charge and can have substituents. n is an integer greater than 1 and less than 3. (Y) C ) Y C The reason for selecting Y C1 and Y C2 One or more of the following groups constitute a 1+n valence group: Y C1It is a directly bonded group composed of one or more groups selected from -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-)2 and -N(-)2 (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10 or 1 to 4 carbon atoms) in each occurrence). Y C2 It is a group composed of one or more of an aliphatic hydrocarbon group with 1 to 40 carbon atoms that may have substituents, an aromatic hydrocarbon ring with 2 to 4 valences that may have substituents, and a heterocycle with 2 to 4 valences that may have substituents.

[0251] n is related to Y C Bonded Z C The number of elements can be an integer between 1 and 3. n can be 1 or higher, 2 or higher, or 3 or higher. n can also be less than 3, less than 2, or less than 1, for example, less than 2.

[0252] Y C The molecular weight can be above 10, above 50, above 100, above 200, above 300, above 500, or above 750, and can be below 3000, below 2500, below 2000, below 1500, below 1000, below 750, below 500, below 300, below 200, below 100, or below 50.

[0253] Y C It may contain at least an amide group, an amino ester group, a urea group, an imide group, a thioamide group, a thioamino ester group, a thiourea group, a thioimide group, a sulfonamide group, a sulfonylurea group, a sulfonamide group, or a sulfonamide group. For example, Y C It can be -C(=O)-NR'-, -O-C(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'-, or -SO2NR'-. Through Y C The presence of these groups improves liquid repellency.

[0254] ○ Y C1 Y C1 It is a non-hydrocarbon linker.

[0255] Y C1 It is a directly bonded group or a group with a divalent or higher valence. Y C1 The valence can be 2–4, 2–3, or 2. Y is preferred. C1 It is not only a direct bond.

[0256] Y C1The molecular weight can be above 10, above 50, above 100, above 200, above 300 or above 500, and can be below 2000, below 1500, below 1000, below 750 or below 500.

[0257] Y C1 It is composed of one or more groups selected from direct bonding, -O-, -C(=O)-, -S(=O)2-, -NR'-, -C(OR')R'-, and -C(OR')(-)2 (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) each time it appears). As Y C1 Examples can be listed as follows: direct bond, -O-、 -O-C (=O)-, -O-C (=O)-O-, -O-C (=O)-NR'-, -NR'-、 -NR'-C(=O)-、 -NR'-C(=O)-O-, -NR'-C (=O)-NR'-, -C (=O)-, -C (=O) -O-, -C(=O)-NR'-, -SO2-, -SO2NR'-, -C(OR')R'-, -C(OR')(-)2 etc.

[0258] (In the formula, R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) each time it appears.) Y C1 It may contain at least an amide group, an amino ester group, a urea group, an imide group, a thioamide group, a thioamino ester group, a thiourea group, a thioimide group, a sulfonamide group, a sulfonylurea group, a sulfonamide group, or a sulfonamide group. For example, Y C1 It can contain -C(=O)-NR'-, -O-C(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'-, or -SO2NR'-. Through Y C1 The presence of these groups improves liquid repellency.

[0259] ○ Y C2 Y C2It is a linker group that can have substituents, aromatic hydrocarbon rings that can have substituents, or heterocyclic rings that can have substituents.

[0260] Y C2 It can be a hydrocarbon group or a non-hydrocarbon group (containing heteroatoms). Y C2 It can be aliphatic or aromatic. C2 It can be linear, branched, or cyclic.

[0261] Y C2 It is a divalent or higher group. Y C2 The valence can be, for example, 2-4, 2-3, or 2.

[0262] Y C2 The number of carbon atoms can 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 can be less than 40, less than 35, less than 30, less than 25, less than 20, less than 15, less than 10, or less than 5.

[0263] Y C2 It is composed of one or more aliphatic hydrocarbon groups with 1 to 40 carbon atoms that may have substituents, aromatic hydrocarbon rings with 2 to 4 valences that may have substituents, and heterocycles with 2 to 4 valences that may have substituents.

[0264] Aliphatic hydrocarbon groups with 1 to 40 carbon atoms and a valence of 2 to 4 can be cyclic, branched, or straight-chain hydrocarbon groups. These groups can be saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon groups. The number of carbon atoms in these groups can be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more, and can be less than 35, less than 30, less than 25, less than 20, less than 15, less than 10, or less than 5. The valence of the aliphatic hydrocarbon group can be 2 or more, 3 or more, or 4, and can be less than 4, less than 3, or 2.

[0265] Aliphatic hydrocarbon groups may have substituents. Examples of substituents include -OR', -N(R')2, -COOR', and halogen atoms (where R' is a hydrocarbon group with 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms each time it appears). Substituents may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In aliphatic hydrocarbon groups with substituents, the amount of carbon atoms 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, relative to the amount of carbon atoms and heteroatoms; and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0266] Examples of aromatic hydrocarbon rings with 2 to 4 valences include groups formed by removing 2 to 4 hydrogen atoms from aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, benzo[a]tetraphenyl (naphthene), pentabenzene, pyrene, and phenanthrene. The number of ring atoms in the aromatic hydrocarbon ring is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valence of the aromatic hydrocarbon ring can be 2 or more, 3 or more, or 4, and can be 4 or less, 3 or less, or 2.

[0267] Aromatic hydrocarbon rings may have substituents. Examples of substituents include -R', -OR', -N(R')2, -COOR', and halogen atoms (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms each time it appears). Substituents may or may not have active hydrogen atoms. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In aromatic hydrocarbon rings with substituents, the amount of carbon atoms 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, relative to the amount of carbon atoms and heteroatoms; and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0268] The 2- to 4-valent heterocycle can be an aliphatic or aromatic group. Examples of 2- to 4-valent heterocycles include groups from pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cyclophosphine, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benziisothiazole, pyrrolidine, piperidine, piperazine, imidazole, thiazoline, etc., which have had 2 to 4 hydrogen atoms removed. The number of cyclic atoms in the heterocycle is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valence of the heterocycle can be 2 or more, 3 or more, or 4, and can be 4 or less, 3 or less, or 2.

[0269] Heterocyclic rings may have substituents. Examples of substituents include -R', -OR', -N(R')2, -COOR', and halogen atoms (where R' is independently a hydrogen atom or a hydrocarbon group with 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms each time it appears). Substituents may or may not have active hydrogen atoms. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In heterocyclic rings with substituents, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, for example, 65 mol% or more; and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less.

[0270] As Y C2 Examples can be listed as follows: -Ali- -Cy- -Ali (-)2 -Cy(-)2 (-)2Ali- (-)2Cy- (-)2Ali (-)2 (-)2Cy(-)2 -Ali-Cy- -Cy-Ali- -Cy-Ali-Cy- -Ali-Cy-Ali- etc.

[0271] [In the formula, Ali is an aliphatic hydrocarbon group with 1 to 20 carbon atoms, and Cy is an aromatic hydrocarbon ring or heterocycle.] As Y C2 Specific examples can be listed as follows: - (CH2)p - (p is 1-40, 1-20, or 1-10) A straight-chain hydrocarbon group with unsaturated bonds, having 1–40, 1–20, or 1–10 carbon atoms. Hydrocarbon groups with branched structures having 1–40, 1–20, or 1–10 carbon atoms - (CH2) q -Cy- (CH2) r - (q and r are independently 0 to 20, for example 1 to 10, and Cy is an aromatic hydrocarbon ring or a heterocyclic ring) etc.

[0272] (Y) C (Example) For Y C Examples will be used to illustrate this. In the following text, R' is independently a hydrocarbon group with 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms) each time it appears.

[0273] As Y C For example, in Y C When it is divalent, we can list -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 -wait.

[0274] As Y C For example, in Y C When it is trivalent, the following can be listed: -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 -Y C1 - ) 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.

[0275] As Y C For example, when Y C is tetravalent, the following can be listed: -Y C1 (-) 3, -Y C1 -YC2 (-)3 -Y C1 -(AND C2 -)3 -Y C1 -AND C2 -AND C1 (-)3 -Y C1 -AND C2 (-AND C1 -)3 -Y C1 -(AND C2 -AND C1 -)3 -Y C1 -AND C2 -AND C1 -AND C2 (-)3 -Y C1 -AND C2 -AND C1 -(AND C2 -) 3、 -AND C1 -AND C2 -(AND C1 -AND C2 -) 3、 -AND C1 -(AND C2 -AND C1 -AND C2 -)3; -AND C2 (-)3 -Y C2 -AND C1 (-)3 -Y C2 -(AND C1 -)3 -Y C2 -AND C1 -AND C2 (-)3 -Y C2 -AND C1 (-AND C2 -)3 -Y C2 -(AND C1 -AND C2 -)3 -Y C2 -AND C1 -AND C2 -AND C1 (-)3 -Y C2 -AND C1 -AND C2 -(AND C1 -) 3、 -AND C2 -AND C1 -(AND C2 -AND C1 -) 3、 -AND C2 -(AND C1 -AND C2 -ANDC1 -) 3, etc.

[0276] As Y C Preferred examples can be listed as -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.

[0277] (Y) C (Preferred example) Y C It can be preferably -Y C11 - or -Y C11 -Y C21 -Y C12 -.

[0278] [In the formula, each symbol appears independently each time.] Y C11 It is either -O- or -NR'-. Y C21 It consists of hydrocarbon groups with 1 to 40 carbon atoms. Y C12 are -O-, -O-C (=O)-, -O-C (=O)-O-, -C (=O)-NR'-, -O-C (=O)-NR'-, -NR'-, -NR'-C (=O)-, -NR'-C (=O)-O- , -NR'-C (=O) -NR'-, -C (=O)-, -C (=O) -O-, -C (=O) -NR'-, -SO2-, -SO2NR'-, -C (OR')R'- or -C (OR') (-)2. ] Y C11 It is a non-hydrocarbon linker, which is a directly bonded or divalent or higher group.

[0279] Y C11 The molecular weight can be above 10, above 50, above 100, above 200, above 300 or above 500, and can be below 2000, below 1500, below 1000, below 750 or below 500.

[0280] Y C11It can be a direct bond, -C(=O)-, -C(=O)-NR'-, or -C(=S)-NR'-.

[0281] Y C21 It is a divalent hydrocarbon linker, which can be a hydrocarbon group with 1 to 40 carbon atoms.

[0282] Y C21 The number of carbon atoms can 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 can be less than 40, less than 35, less than 30, less than 25, less than 20, less than 15, less than 10, or less than 5.

[0283] Here, the hydrocarbon group with 1 to 40 carbon atoms can be a cyclic, branched, or straight-chain hydrocarbon group, and can be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group.

[0284] As Y C21 Specific examples can be listed as follows: - (CH2) p - (p is 1-40, 1-20, or 1-10) A straight-chain hydrocarbon group with unsaturated bonds, having 1–40, 1–20, or 1–10 carbon atoms. Hydrocarbon groups with branched structures having 1–40, 1–20, or 1–10 carbon atoms - (CH2) q -Cy- (CH2) r - (q and r are independently 0 to 20, for example 1 to 10, and Cy is an aromatic hydrocarbon ring or a heterocyclic ring) etc.

[0285] Y C12 Can be -O-, -O-C(=O)-, -O-C(=O)-O-, -O-C(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR' -C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO2-, -SO2NR'-, -C(OR')R'- or -C(OR')(-)2.

[0286] Y C12 It may contain at least an amide group, an amino ester group, a urea group, an imide group, a thioamide group, a thioamino ester group, a thiourea group, a thioimide group, a sulfonamide group, a sulfonylurea group, a sulfonamide group, or a sulfonamide group. For example, Y C12 It can be -C(=O)-NR'-, -O-C(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'-, or -SO2NR'-. Through YC12 The presence of these groups improves liquid repellency.

[0287] (Z) C ) Z C For a hydrocarbon group that can have a monovalent carbon number of 6 to 40 and may have substituents, the explanation in the above (hydrocarbon groups that can have substituents) is followed.

[0288] [Other modifying groups] The hydroxyl group of a polycarboxylic acid can be -Y C -Z C n Other modifying groups may be substituted. Examples of modifying groups include anionic and / or cationic groups. As for anionic and / or cationic groups, the description of [other modifying groups] in the above polyols shall continue.

[0289] [Manufacturing Method] Polycarboxylic acid modifiers can be manufactured by reacting a modifier having a modifying group (or a precursor structure of the modifying group) with the hydroxyl group of a polycarboxylic acid.

[0290] (Polycarboxylic acids) Polycarboxylic acids are compounds with two or more carboxyl groups, and are the starting materials for polycarboxylic acid modifiers. A polycarboxylic acid is defined as a compound having two or more carboxyl groups within its molecule. Polycarboxylic acids can be aliphatic or aromatic, with aliphatic being preferred.

[0291] Polycarboxylic acids can be low molecular weight (e.g., weight average molecular weight less than 1000, below 500) and / or high molecular weight. The weight average molecular weight of polycarboxylic acids can be above 100, above 300, above 500, above 1000, above 3000, above 5000, above 10000, above 30000, above 100000, above 300000, or above 500000, and can be below 1000000, below 7500000, below 500000, below 300000, below 100000, below 75000, below 50000, below 30000, below 10000, below 5000, below 3000, below 2000, below 1000, or below 500.

[0292] The number of carboxyl groups in a polycarboxylic acid can 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 can be less than 3000, less than 1000, less than 750, less than 500, less than 300, less than 100, less than 50, less than 30, or less than 20.

[0293] The carboxyl equivalent of a polycarboxylic acid can be greater than 20, greater than 40, greater than 60, greater than 80, greater than 100, greater than 120, or greater than 150, and can also be less than 1000, less than 800, less than 600, less than 400, less than 200, less than 100, or less than 75. The carboxyl equivalent of a polycarboxylic acid is the value obtained by dividing the weight-average molecular weight of the polycarboxylic acid by the number of hydroxyl groups.

[0294] Polycarboxylic acids can be natural products. These natural products can be high-molecular-weight natural products, low-molecular-weight natural products, or their derivatives. Compounds transformed by microorganisms are also included among these natural products.

[0295] The polycarboxylic acid can be at least one selected from dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids, carboxyl-containing polymers, and their salts.

[0296] Dicarboxylic acids are compounds that have two carboxyl groups, such as oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, phthalic acid, terephthalic acid, malic acid, tartaric acid, aldonic acid, and their salts.

[0297] Tricarboxylic acids are compounds with three carboxyl groups, such as citric acid, procarboxylic acid, trans-aconitic acid, trimellitic acid, and their salts.

[0298] Tetracarboxylic acids are compounds with four carboxyl groups, such as pyromellitic acid and its salts.

[0299] Carboxyl-containing polymers are compounds with 5 or more carboxyl groups, such as alginate, tragacanth gum, gum arabic, polyacrylic acid, polymethacrylic acid, polymaleic acid, polyaspartic acid, polyglutamic acid, hyaluronic acid, heparin, xanthan gum, gellan gum, alginate carboxymethyl cellulose, galacturonic acid, mannouronic acid, and their salts.

[0300] (Modifier) The modifier is a compound that is reactive with polycarboxylic acids, preferably the above-mentioned compound containing a hydrocarbon group with a monovalent carbon atom number of 6 to 40 that may have substituents.

[0301] Examples of modifiers are as follows.

[0302] Epoxy (CH2OCH)CH2O-Z C Amine H2N-Z C Hydroxyl HO-Z C [In the formula, Z] C As above.

[0303] The Z in the structure of the above-mentioned modifiers can also be... CReplace it with any group that constitutes the modifying group; for example, Z can be made C It can be a hydrocarbon group with a monovalent carbon number of 6 to 40 that can have substituents, for example, it can be a Z-type hydrocarbon group. C For -Y C -Z C n .

[0304] Polycarboxylic acid modifiers can be synthesized by reacting polycarboxylic acids with modifying agents. For example, reacting an epoxy compound as a modifying agent with the carboxyl group of a polycarboxylic acid to form an ester bond can generate a polycarboxylic acid modifier. Those skilled in the art can design appropriate reaction conditions for the polycarboxylic acid and the modifying agent based on the target product, using catalysts (e.g., acid catalysts, base catalysts), condensing agents, etc.

[0305] [Dispersant] The dispersant of the present invention may contain a dispersant. The dispersant may be at least one selected from organic dispersants and inorganic dispersants. The dispersant may be at least one selected from anionic dispersants, nonionic dispersants, cationic dispersants, amphoteric dispersants and inorganic dispersants.

[0306] Dispersants can be organic dispersants and inorganic dispersants, or a combination of organic and inorganic dispersants.

[0307] Organic dispersants can be used as dispersants. Organic dispersants can be classified into nonionic dispersants, anionic dispersants, cationic dispersants, and amphoteric dispersants. Organic dispersants are essentially surfactants.

[0308] The dispersant can be a non-fluorinated dispersant.

[0309] [Nonionic dispersant] Dispersants may include nonionic dispersants. Nonionic dispersants may be nonionic surfactants.

[0310] Nonionic dispersants can be either low molecular weight or high molecular weight. Molecular weight can be above 100, above 500, above 1000, above 2000, above 4000, or above 6000, and can also be below 100000, below 10000, below 7500, below 5000, below 25000, below 750, or below 250.

[0311] Examples of nonionic dispersants include ethers, esters, ester ethers, alkanolamides, polyols, and amine oxides.

[0312] Examples of ethers include compounds having oxyalkylene groups (preferably polyoxyethylene groups).

[0313] Examples of esters include esters of alcohols and fatty acids. Examples of alcohols include 1- to 30-membered (especially 2- to 10-membered) alcohols with 1 to 50 carbon atoms (especially 10 to 30 carbon atoms), such as aliphatic alcohols. Examples of fatty acids include saturated or unsaturated fatty acids with 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

[0314] Examples of ester ethers include compounds formed by the addition of alkyl epoxides (especially ethylene oxide) to the esters of alcohols and fatty acids. Examples of alcohols include 1- to 30-membered (especially 2- to 10-membered) alcohols (e.g., aliphatic alcohols) with 1 to 50 carbon atoms (especially 3 to 30 carbon atoms). Examples of fatty acids include saturated or unsaturated fatty acids with 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

[0315] Examples of alkanolamides are formed from fatty acids and alkanolamines. Alkanolamides can be monoalkanolamides or dialkanolamides. Examples of fatty acids are saturated or unsaturated fatty acids with 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. Alkanolamines can be alkanols with 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0316] Polyols can be 2 to 5-membered alcohols with 10 to 30 carbon atoms.

[0317] The amine oxide can be an oxide of an amine (secondary amine or preferably tertiary amine) (e.g., having 5 to 50 carbon atoms).

[0318] The nonionic dispersant is preferably a nonionic dispersant having an alkylene oxide (preferably polyoxyethylene). The number of carbon atoms in the alkylene oxide is preferably 2 to 10. The number of alkylene oxides in the molecule of the nonionic dispersant is generally preferably 2 to 100.

[0319] The nonionic dispersant is selected from ethers, esters, ester ethers, alkanolamides, polyols and amine oxides, and is preferably a nonionic dispersant with oxyalkylene groups.

[0320] Nonionic dispersants can be alkylene oxide adducts of linear and / or branched aliphatic (saturated and / or unsaturated) groups, polyalkylene glycol esters of linear and / or branched fatty acids (saturated and / or unsaturated), dehydrated sorbitol esters of linear and / or branched fatty acids (saturated and / or unsaturated), glycerides of linear and / or branched fatty acids (saturated and / or unsaturated), polyglycerol esters of linear and / or branched fatty acids (saturated and / or unsaturated), sucrose esters of linear and / or branched fatty acids (saturated and / or unsaturated), polyoxyethylene (POE) / polyoxypropylene (POP) copolymers (random copolymers or block copolymers), alkylene glycol alkylene oxide adducts, etc. Among these, the preferred structures of the alkylene oxide addition portion and the polyalkylene glycol portion are polyoxyethylene (POE), polyoxypropylene (POP), or POE / POP copolymers (which can be random copolymers or block copolymers).

[0321] In addition, nonionic dispersants may not contain aromatic groups.

[0322] Nonionic dispersants can be of the following formula: R 1 O-(CH2CH2O) p - (R) 2 O) q -R 3 The compound shown.

[0323] [In the formula, R] 1 It is an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or an acyl group. Each R 2 Independent, can be the same or different, and is an alkylene group with 3 or more carbon atoms (e.g., 3 to 10). R 3 It consists of hydrogen atoms, alkyl groups having 1 to 22 carbon atoms, or alkenyl groups having 2 to 22 carbon atoms. p is a number greater than or equal to 2. q is a number that is 0 or greater than 1. R 1 Preferably, the number of carbon atoms is 8–20, particularly 10–18. As R… 1 Preferred specific examples may include octyl, nonyl, trimethylnonyl, lauryl, tridecyl, oleyl, and stearyl.

[0324] R 2 Examples include propylidene and butylidene.

[0325] In nonionic dispersants, p can be a number greater than 3 (e.g., 5–200). q can be a number greater than 2 (e.g., 5–200). That is, -(R 2 O) q- It can form polyoxyalkylene chains.

[0326] The nonionic dispersant can be a polyoxyethylene alkylene ether having a central hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (especially a polyoxyalkylene chain). Examples of hydrophobic oxyalkylene chains include oxypropylene chains, oxybutylene chains, and styrene chains, with oxypropylene chains being preferred.

[0327] Specific examples of nonionic dispersants include: ethylene oxide with hexylphenol, isooctylphenol, hexadecyl alcohol, oleic acid, and alkyl groups (C... 12 -C 16 Thiols, sorbitol monofatty acids (C7-C5) 19 ) or alkyl (C 12 -C 18 Condensation products of amines, etc., dehydrated sorbitol fatty acid esters, glycerol fatty acid esters, polyglycerol fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene glycerol fatty acid esters, polyoxyethylene dehydrated sorbitol 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, polyoxyethylene imine ethoxylates, etc.

[0328] The proportion of polyoxyethylene blocks relative to the molecular weight of the nonionic dispersant (copolymer) can be 5 to 80% by weight, for example 30 to 75% by weight, and particularly 40 to 70% by weight.

[0329] The average molecular weight of nonionic dispersants is typically 300–5000, for example, 500–3000.

[0330] Nonionic dispersants can be a single type or a mixture of two or more. Nonionic dispersants can be mixtures of compounds with an HLB (hydrophilicity-hydrophobicity balance) of less than 15 (particularly less than 5) and compounds with an HLB of 15 or more. Specifically, preferred dispersants are polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyethylene oxide, polyoxypropylene, or dehydrated sorbitol fatty acid esters, glycerol fatty acid esters, polyglycerol fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene glycerol fatty acid esters, and polyoxyethylene dehydrated sorbitol fatty acid esters with an HLB of 1 to 18.

[0331] [Catonic dispersant] Dispersants may include cationic dispersants. Cationic dispersants may be cationic surfactants. Cationic dispersants may be compounds without amide groups.

[0332] Cationic dispersants can be low molecular weight (e.g., molecular weight below 2000, especially below 10000) or high molecular weight (e.g., molecular weight above 2000). The molecular weight of cationic dispersants can be above 100, above 500, above 1000, above 2000, above 4000, or above 6000, and can be below 1,000,000, below 750,000, below 500,000, below 250,000, below 100,000, below 50,000, below 10,000, below 7,500, below 5,000, below 25,000, below 750, or below 250.

[0333] Cationic dispersants can be aliphatic or aromatic, and examples include ammonium salts (such as quaternary ammonium salts). Cationic dispersants can be addition-type ammonium salts of ethylene oxide. Specifically, examples include: amine salt dispersants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazoline; quaternary ammonium salt dispersants such as alkyl trimethylammonium salts, dialkyl dimethylammonium salts, alkyl dimethyl benzylammonium salts, pyridinium salts, alkyl isoquinoline onion salts, benzalkonium chloride, and benzyl chloride; and high-molecular-weight cationic dispersants such as polyquaternium salts-1 to 47. Examples of cationic dispersants include alkylamine salts and quaternary ammonium salts.

[0334] Low molecular weight cationic dispersants can be R 21 -N ＋ (-R) 22 (-R) 23 (-R) 24 )X － The compound shown.

[0335] [In the formula, R] 21 R 22 R 23 and R 24 It consists of 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, palmityl), aromatic groups (e.g., benzyl, phenyl), etc. Specific examples of X include halogens (e.g., chlorine), acids (e.g., hydrochloric acid, acetic acid), etc. Examples of cationic dispersants include monoalkyl trimethylammonium salts (alkyl groups with 4 to 40 carbon atoms) and benzalkonium chloride, etc.

[0336] Specifically, low-molecular-weight cationic dispersants can be of the following formula: R 1 p -N＋ R 2 q X － The ammonium salt shown.

[0337] [In the formula, R] 1 For C12 and above (e.g., C 12 ~C 50 Straight-chain and / or branched aliphatic (saturated and / or unsaturated) groups, R 2 It is an alkyl group, benzyl group, or polyoxyethylene group (with an oxyethylene number of, for example, 1 (especially 2, especially 3) to 50) of H or C1 to 4 (particularly preferred CH3, C2H5). X is a halogen atom (e.g., chlorine), a C1-C4 fatty acid salt, or a C1-C4 sulfonate. p is 1 or 2, q is 2 or 3, and p + q = 4. R 1 The number of carbon atoms can be 12 to 50, for example, 12 to 30.

[0338] Low molecular weight cationic dispersants may include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyl di(hydroxypolyoxyethylene)ammonium chloride, benzyldodecyl di(hydroxypolyoxyethylene)ammonium chloride, N-[2-(diethylamino)ethyl]oleamide hydrochloride, etc.

[0339] High molecular weight cationic dispersants can be various polymers (e.g., polyquaternium salts-1 to 47) containing cationic groups (e.g., ammonium groups, quaternary ammonium groups). Examples of high molecular weight cationic dispersants include: cationic starch, cationic cellulose (e.g., O-(2-hydroxy-3-(trimethylammonium)propylhydroxyethyl cellulose chloride), cationic guar gum, cationic xanthan gum, chitosan, and other cationic natural products (especially cationic sugars); polymers of monomers containing cationic groups such as aziridine, vinylimidazole, aminoalkyl methacrylate, N,N,N',N'-tetramethyl-2-butene-1,4-diamine, dimethylammonium quaternized ethyl methacrylate, diallyl dimethylammonium chloride, dimethylaminopropylamine, and quaternized vinylimidazole.

[0340] [Anionic dispersant] Dispersants may contain anionic dispersants. Anionic dispersants may be anionic surfactants. Dispersants may also not contain anionic dispersants.

[0341] Anionic dispersants can be low molecular weight or high molecular weight. Molecular weight can be above 100, above 500, above 1000, above 2000, above 4000, or above 6000, and can also be below 100000, below 10000, below 7500, below 5000, below 25000, below 750, or below 250.

[0342] Examples of anionic dispersants include: alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfonyl fatty acid salts, N-acyl amino acid type dispersants, phosphate monoester or diester type dispersants, and sulfosuccinates. Examples of anionic dispersants include carboxylates (e.g., fatty acid salts).

[0343] [Amphoteric Dispersant] Dispersants may include amphoteric dispersants. Amphoteric dispersants may be amphoteric surfactants.

[0344] Amphoteric dispersants can be either low molecular weight or high molecular weight. Molecular weight can be above 100, above 500, above 1000, above 2000, above 4000, or above 6000, and can also be below 100000, below 10000, below 7500, below 5000, below 25000, below 750, or below 250.

[0345] Examples of amphoteric dispersants include: alanine derivatives, imidazoline betaines, amide betaines, and acetate betaines. More specifically, examples include: lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazoline betaine, lauryl dimethyl aminoacetic acid betaine, and fatty acid amide propyl dimethyl aminoacetic acid betaine.

[0346] [Inorganic dispersant] Dispersants may include inorganic dispersants.

[0347] The average primary particle size of inorganic dispersants can be greater than 5 nm, greater than 30 nm, greater than 100 nm, greater than 1 μm, greater than 10 μm, or greater than 25 μm, and can also be less than 100 μm, less than 50 μm, less than 10 μm, less than 1 μm, less than 500 nm, or less than 300 nm. The average primary particle size can be determined, for example, by observation using a microscope (scanning electron microscope or transmission electron microscope). Inorganic dispersants can be hydrophilic particles.

[0348] Examples of inorganic dispersants include: tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, hydroxyapatite and other polyvalent metal salts of phosphate; calcium carbonate, magnesium carbonate and other carbonates; calcium metasilicate and other silicates; calcium sulfate, barium sulfate and other sulfates; calcium hydroxide, magnesium hydroxide, aluminum hydroxide and other hydroxides, etc.

[0349] [Amount of dispersant] The amount of dispersant relative to 100 parts by weight of the liquid-repellent compound can be more than 0.01 parts by weight, more than 0.1 parts by weight, more than 1 part by weight, more than 3 parts by weight, more than 5 parts by weight, more than 10 parts by weight, more than 15 parts by weight, more than 20 parts by weight, more than 50 parts by weight, more than 75 parts by weight, or more than 100 parts by weight, and can be less than 500 parts by weight, less than 300 parts by weight, less than 200 parts by weight, less than 100 parts by weight, less than 30 parts by weight, less than 20 parts by weight, less than 10 parts by weight, less than 5 parts by weight, less than 3 parts by weight, or less than 1 part by weight.

[0350] [Liquid medium] The dispersant of the present invention may contain a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The dispersant may be a dispersion or a solution. The dispersant of the present invention contains at least water.

[0351] Examples of organic solvents include esters (e.g., esters with 2 to 40 carbon atoms, specifically ethyl acetate and butyl acetate), ketones (e.g., ketones with 2 to 40 carbon atoms, specifically methyl ethyl ketone and diisobutyl ketone), alcohols (e.g., alcohols with 1 to 40 carbon atoms, specifically isopropanol), aromatic solvents (e.g., toluene and xylene), and petroleum-based solvents (e.g., alkanes with 5 to 10 carbon atoms, specifically naphtha and kerosene). Water-soluble organic solvents are preferred. Water-soluble organic solvents may also contain compounds having at least one hydroxyl group (e.g., alcohols, diols, polyols, ethers of polyols (e.g., monoethers)). They can be used alone or in combination of two or more.

[0352] [Amount of liquid medium] The amount of liquid medium relative to 1 part by weight of the repellent compound can be more than 1 part by weight, more than 3 parts by weight, more than 5 parts by weight, more than 10 parts by weight, more than 20 parts by weight, more than 30 parts by weight, more than 40 parts by weight, or more than 50 parts by weight, more than 100 parts by weight, more than 200 parts by weight, more than 300 parts by weight, more than 500 parts by weight, or more than 1000 parts by weight, and can be less than 3000 parts by weight, less than 2000 parts by weight, less than 1000 parts by weight, less than 500 parts by weight, less than 200 parts by weight, less than 175 parts by weight, less than 150 parts by weight, less than 125 parts by weight, less than 100 parts by weight, less than 80 parts by weight, less than 60 parts by weight, less than 40 parts by weight, less than 20 parts by weight, or less than 10 parts by weight.

[0353] The amount of water relative to 1 part by weight of the liquid-repellent compound can be more than 1 part by weight, more than 3 parts by weight, more than 5 parts by weight, more than 10 parts by weight, more than 20 parts by weight, more than 30 parts by weight, more than 40 parts by weight, more than 50 parts by weight, more than 100 parts by weight, more than 200 parts by weight, more than 300 parts by weight, more than 500 parts by weight, or more than 1000 parts by weight, and can be less than 3000 parts by weight, less than 2000 parts by weight, less than 1000 parts by weight, less than 500 parts by weight, less than 200 parts by weight, less than 175 parts by weight, less than 150 parts by weight, less than 125 parts by weight, less than 100 parts by weight, less than 80 parts by weight, less than 60 parts by weight, less than 40 parts by weight, less than 20 parts by weight, or less than 10 parts by weight.

[0354] The amount of organic solvent relative to 1 part by weight of the liquid-repellent compound can be more than 1 part by weight, more than 3 parts by weight, more than 5 parts by weight, more than 10 parts by weight, more than 20 parts by weight, more than 30 parts by weight, more than 40 parts by weight, more than 50 parts by weight, more than 100 parts by weight, more than 200 parts by weight, more than 300 parts by weight, more than 500 parts by weight, or more than 1000 parts by weight, and can be less than 3000 parts by weight, less than 2000 parts by weight, less than 1000 parts by weight, less than 500 parts by weight, less than 200 parts by weight, less than 175 parts by weight, less than 150 parts by weight, less than 125 parts by weight, less than 100 parts by weight, less than 80 parts by weight, less than 60 parts by weight, less than 40 parts by weight, less than 20 parts by weight, or less than 10 parts by weight.

[0355] 〔wax〕 The repellent of the present invention may contain wax. By containing wax, it is possible to impart good repellency to the substrate.

[0356] Examples of waxes include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin wax (polyethylene wax, polypropylene wax, etc.), oxidized polyolefin wax, silicone wax, animal and plant waxes, and mineral waxes. Paraffin wax is preferred. Specific examples of compounds constituting waxes include n-alkanes (e.g., tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, triacontane, triacontane, dodecane, tridecane, tetradecane, pentadecane, hexadecane), and n-olefins (e.g., 1-eicosene, 1-diene, 1-tetratene, 1-tetradecene, 1-pentadecane, 1-hexadecene, 1-heptadecene, 1-octadecene, nonacontene, triacontene, dodecanene, triterpenesene, tetradecene, pentadecene, hexadecene). The number of carbon atoms in the compounds constituting waxes is preferably 20 to 60, for example, 25 to 45. The molecular weight of waxes can range from 200 to 2000, for example 250 to 1500, or 300 to 1000. They can be used alone or in combination of two or more.

[0357] The melting point of the wax can be above 50°C, above 55°C, above 60°C, above 65°C, or above 70°C, preferably above 55°C, and more preferably above 60°C. The melting point of the wax is determined according to JIS K 2235-1991.

[0358] [Amount of wax] The amount of wax relative to 100 parts by weight of the repellent compound can 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. The amount of wax relative to 100 parts by weight of the repellent compound can be less than 500 parts by weight, less than 300 parts by weight, less than 200 parts by weight, less than 100 parts by weight, less than 50 parts by weight, less than 40 parts by weight, less than 30 parts by weight, less than 20 parts by weight, less than 10 parts by weight, or less than 5 parts by weight.

[0359] [Organosilicon] The repellent of this invention may contain organosilicon (polyorganosiloxane). By containing organosilicon, in addition to good repellency, it can also provide good feel and durability.

[0360] As organosilicones, known organosilicones can be used. Examples of organosilicones include polydimethylsiloxane and modified organosilicones (amino-modified, epoxy-modified, carboxyl-modified, methylhydrosilicon, etc.). Organosilicones can be silicone waxes with waxy properties. They can be used alone or in combination of two or more.

[0361] The weight-average molecular weight of organosilicon can be above 1000, above 10000, or above 50000, and can also be below 500000, below 2500000, below 100000, or below 50000.

[0362] [Amount of organosilicon] The amount of organosilicon can be more than 0.1 parts by weight, more than 1 part by weight, more than 3 parts by weight, more than 5 parts by weight, more than 10 parts by weight, more than 15 parts by weight, more than 20 parts by weight, more than 50 parts by weight, more than 75 parts by weight, or more than 100 parts by weight, and can be less than 500 parts by weight, less than 300 parts by weight, less than 200 parts by weight, less than 100 parts by weight, less than 50 parts by weight, less than 40 parts by weight, less than 30 parts by weight, less than 20 parts by weight, less than 10 parts by weight, or less than 5 parts by weight, relative to 100 parts by weight of the liquid-repellent compound.

[0363] [Organic acids] The dissolving agent of the present invention may contain an organic acid. Known organic acids can be used as the organic acid. Carboxylic acids, sulfonic acids, sulfinic acids, etc., are preferred examples of the organic acid, with carboxylic acids being particularly preferred. Examples of the carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid, etc., with formic acid or acetic acid being particularly preferred. In the present invention, one organic acid may be used, or two or more may be used in combination. For example, formic acid and acetic acid may be used in combination.

[0364] [Amount of organic acids] The amount of organic acid relative to 100 parts by weight of the repellent compound can 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 can be less than 500 parts by weight, less than 300 parts by weight, less than 200 parts by weight, less than 100 parts by weight, less than 50 parts by weight, less than 40 parts by weight, less than 30 parts by weight, less than 20 parts by weight, less than 10 parts by weight, or less than 5 parts by weight. The amount of organic acid can be adjusted so that the pH of the repellent reaches 3 to 10, for example 5 to 9, especially 6 to 8. The repellent can be acidic (pH 7 or below, for example, below 6).

[0365] [Inorganic acids] The dispersant of the present invention may contain an inorganic acid. Known inorganic acids can be used as the inorganic acid. Examples of inorganic acids include hydrogen chloride, hydrogen bromide, hydrogen iodide, nitric acid, boric acid, sulfuric acid, and phosphoric acid. In the present invention, one inorganic acid or a combination of two or more can be used. By adding an inorganic acid, the stability of the aqueous dispersion can be improved.

[0366] [Amount of inorganic acid] The amount of inorganic acid relative to 100 parts by weight of the repellent compound can 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 can be less than 500 parts by weight, less than 300 parts by weight, less than 200 parts by weight, less than 100 parts by weight, less than 50 parts by weight, less than 40 parts by weight, less than 30 parts by weight, less than 20 parts by weight, less than 10 parts by weight, or less than 5 parts by weight. The amount of inorganic acid can be adjusted so that the pH of the repellent reaches 3 to 10, for example 5 to 9, especially 6 to 8. The repellent can be acidic (pH 7 or below, for example, below 6).

[0367] [Curing agent] The release agent of the present invention may contain a curing agent (an active hydrogen reactive compound or a compound containing active hydrogen).

[0368] The curing agent (crosslinking agent) in the release agent enables it to cure well. The curing agent can be an active hydrogen reactive compound, or a compound containing active hydrogen, capable of reacting with active hydrogen or active hydrogen reactive groups. Examples of active hydrogen reactive compounds include isocyanate compounds, epoxy compounds, chloromethyl-containing compounds, carboxyl-containing compounds, and acylhydrazine compounds. Examples of compounds containing active hydrogen include hydroxyl-containing compounds, amino-containing compounds, carboxyl-containing compounds, ketone-containing compounds, acylhydrazine compounds, and melamine compounds.

[0369] Curing agents can contain isocyanate compounds. Isocyanate compounds can be polyisocyanate compounds. Polyisocyanate compounds are compounds having two or more isocyanate groups in one molecule. Polyisocyanate compounds act as crosslinking agents. Examples of polyisocyanate compounds include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic aliphatic polyisocyanates, aromatic polyisocyanates, and their derivatives. Isocyanate compounds can also be end-capped isocyanate compounds (e.g., end-capped polyisocyanate compounds). End-capped isocyanate compounds are compounds in which the isocyanate groups of the isocyanate compound are masked by a end-capping agent, thereby inhibiting the reaction.

[0370] Examples of aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate or 2,2,4-trimethylhexamethylene diisocyanate, 2,6- Aliphatic diisocyanates such as diisocyanate-methylhexanoate, as well as aliphatic triisocyanates such as lysine ester triisocyanates, 1,4,8-triisocyanate-octane, 1,6,11-triisocyanate-undecane, 1,8-diisocyanate-4-isocyanate-methyloctane, 1,3,6-triisocyanate-hexane, and 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanate-methyloctane, etc. They can be used alone or in combination of two or more.

[0371] Examples of alicyclic polyisocyanates include alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of alicyclic polyisocyanates include 1,3-cyclopentene diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isoflurone diisocyanate), and 1,3,5-triisocyanate cyclohexane. They can be used alone or in combination of two or more.

[0372] Examples of aromatic aliphatic polyisocyanates include aromatic aliphatic diisocyanates and aromatic aliphatic triisocyanates. Specific examples of aromatic aliphatic polyisocyanates include 1,3-phenylenedimethyl diisocyanate or 1,4-phenylenedimethyl diisocyanate or mixtures thereof, 1,3-bis(1-isocyano-1-methylethyl)benzene or 1,4-bis(1-isocyano-1-methylethyl)benzene (tetramethylphenyldimethyl diisocyanate) or mixtures thereof, and 1,3,5-triisocyanomethylbenzene. They can be used alone or in combination of two or more.

[0373] Examples of aromatic polyisocyanates include aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates include m-phenylene diisocyanate, terephthalene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4'-diphenylmethane diisocyanate or 4,4'-diphenylmethane diisocyanate or mixtures thereof, 2,4-toluene diisocyanate or 2,6-toluene diisocyanate or mixtures thereof, triphenylmethane-4,4',4''-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate, etc. They can be used alone or in combination of two or more.

[0374] Derivatives of polyisocyanates include, for example, various derivatives of the aforementioned polyisocyanate compounds such as dimers, trimers, biurets, urethanes, carbodiimides, urea diketones, urea imides, isocyanurates, and iminooxadiazine diketones. They can be used alone or in combination of two or more.

[0375] These polyisocyanates can be used alone or in combination of two or more.

[0376] As a polyisocyanate compound, it is preferable to use a compound in which the isocyanate group of the polyisocyanate compound is capped by a capping agent, i.e., a capped polyisocyanate compound (capped isocyanate). Capped polyisocyanate compounds are preferred because they are relatively stable in solution and can be used in the same solution as the capping agent.

[0377] End-capping agents are substances that seal free isocyanate groups. By heating polyisocyanate compounds to, for example, above 100°C or 130°C, the isocyanate groups can be regenerated and readily react with hydroxyl groups. Examples of end-capping agents include phenolic compounds, lactam compounds, aliphatic alcohol compounds, and oxime compounds. Polyisocyanate compounds can be used alone or in combination of two or more.

[0378] Epoxides are compounds that contain epoxy groups. Examples of epoxy compounds include: epoxy compounds containing polyoxyalkylene groups, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether, etc.

[0379] Compounds containing chloromethyl groups are compounds that have a chloromethyl group present in their structure. Examples of compounds containing chloromethyl groups include chloromethyl polystyrene.

[0380] Compounds containing a carboxyl group are compounds that have a carboxyl group. Examples of compounds containing a carboxyl group include (poly)acrylic acid and (poly)methacrylic acid.

[0381] Specific examples of compounds containing ketone groups include (poly)diacetone acrylamide and diacetone alcohol.

[0382] Specific examples of acylhydrazide compounds include hydrazine, carbazide, and adipic hydrazide.

[0383] Specific examples of melamine compounds include melamine resins and methyl etherified melamine resins.

[0384] [Amount of curing agent] The amount of curing agent relative to 100 parts by weight of the liquid-repellent compound can be more than 0.1 parts by weight, more than 1 part by weight, more than 3 parts by weight, more than 5 parts by weight, more than 10 parts by weight, more than 15 parts by weight, or more than 20 parts by weight, more than 50 parts by weight, more than 75 parts by weight, or more than 100 parts by weight, and can be less than 500 parts by weight, less than 300 parts by weight, less than 200 parts by weight, less than 100 parts by weight, less than 50 parts by weight, less than 40 parts by weight, less than 30 parts by weight, less than 20 parts by weight, less than 10 parts by weight, or less than 5 parts by weight.

[0385] [Other ingredients] The release agent may contain other ingredients besides those mentioned above. Examples of other ingredients include polysaccharides, paper strength enhancers, coagulants, retention aids, binders, adhesive resins, antislip agents, sizing agents, paper strength enhancers, fillers, antistatic agents, preservatives, UV absorbers, antibacterial agents, deodorizers, and fragrances. They can be used alone or in combination of two or more. In addition to the above-mentioned ingredients, other components may be added as follows: water-repellent and / or oil-repellent agents, dispersants, hand feel modifiers, softeners, flame retardants, paint fixatives, anti-wrinkle agents, drying speed modifiers, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, ultraviolet absorbers, antioxidants, pH adjusters, insect repellents, defoamers, anti-shrinkage agents, washing anti-wrinkle agents, shape-retaining agents, drape-retaining agents, ironing enhancers, whitening agents, fabric softening clays, anti-staining agents for polyvinylpyrrolidone, etc., polymeric dispersants, dirt removers, scum dispersants, and 4,4-bis(2-sulfostylenyl)biphenyl disodium (TINOPAL, manufactured by Ciba Specialty Chemicals). Fluorescent whitening agents such as CBS-X, dye fixatives, anti-fading agents such as 1,4-bis(3-aminopropyl)piperazine, bleaching agents, enzymes such as cellulase, amylase, protease, lipase, and keratinase used as fiber surface modifiers, antifoaming agents, silk protein powders that impart the feel / function of silk, such as moisture absorption and release properties, their surface modifiers or emulsion dispersions (e.g., K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical), hydrolyzed silk solution (hair application), SILKGEN G Soluble S (ICHIMARU PHARCOS Co., Ltd.)), anti-fouling agents (e.g., nonionic polymers composed of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units (e.g., FR627 manufactured by Muyo Chemical Industry, SRC-1 manufactured by CLARIANT Japan), etc. They can be used individually or in combination.

[0386] [Amount of other ingredients] Relative to 100 parts by weight of the liquid-repellent compound, the amount or total amount of each of the other components can be more than 0.1 parts by weight, more than 1 part by weight, more than 3 parts by weight, more than 5 parts by weight, more than 10 parts by weight, more than 15 parts by weight, more than 20 parts by weight, more than 50 parts by weight, more than 75 parts by weight, or more than 100 parts by weight, and can be less than 500 parts by weight, less than 300 parts by weight, less than 200 parts by weight, less than 100 parts by weight, less than 50 parts by weight, less than 40 parts by weight, less than 30 parts by weight, less than 20 parts by weight, less than 10 parts by weight, or less than 5 parts by weight.

[0387] <Method for manufacturing pulp compositions / pulp products> The pulp composition of the present invention can be obtained by treating a pulp substrate with a liquid-repellent agent containing a liquid-repellent compound.

[0388] The obtained pulp composition is subjected to processing steps such as drying, heating, and molding as needed to obtain pulp products.

[0389] The release agent of the present invention can be applied to pulp substrates as a treatment agent (especially a surface treatment agent) using existing known methods. As a treatment method, the release agent of the present invention can be diluted by dispersing it in an organic solvent or water as needed, and then adhered to the interior and / or surface of the pulp substrate using known methods such as dip coating, spraying, or blister coating, followed by drying. The dilution ratio can be appropriately varied depending on the concentration or application of the release agent, and can be 3 to 2000 times, for example, 10 to 100 times. After drying, a pulp product with a solid component coated with the release agent can be obtained. Furthermore, it can also be applied together with a suitable crosslinking agent for curing as needed.

[0390] The repellent agent can be applied to the pulp substrate using any known method for treating the pulp substrate with a liquid. The pulp substrate can be immersed in the repellent agent, mixed with the repellent agent, or the solution can be adhered to or sprayed onto the pulp substrate. To induce the treated pulp substrate to exhibit repellency, drying and curing by heating are preferred. Heating temperatures can be, for example, 100°C–200°C, 100°C–170°C, or 100°C–120°C. In this invention, the heating time can be from 5 seconds to 60 minutes, for example, from 30 seconds to 3 minutes.

[0391] As a method for treating pulp substrates, internal processing methods can be employed, such as adding a dispersant to the pulp substrate before papermaking (e.g., the form of pulp slurry), or external processing methods, such as applying a dispersant to the pulp substrate after papermaking (e.g., pulp products). Examples of internal processing methods include mixing and impregnation, which may involve adding a dispersant to the pulp slurry and then mixing it. Examples of external processing methods include spraying, coating, impregnation, and blister coating, specifically including sizing presses with glue tanks, weir rolls, and metering rods. The treatment can be either internal or external. For example, when the pulp substrate is paper, it can be coated onto the paper, applied to the paper, sprayed, or mixed with the pulp slurry before papermaking. When the pulp substrate is a fibrous material, processing methods include, for example, pad dyeing, impregnation, spraying, and coating. For pad dyeing, methods using pad dyeing apparatuses described in the *Dictionary of Fiber Dyeing Processing* (published by Nikkan Kogyo Shimbun in 1963) and *Dyeing Chemistry III* (published by Jitsukyo Publishing Co., Ltd. in 1975) can be cited as examples. For coating, methods using coating machines described in the *Overview of Dyeing Finishing Equipment* (published by Kogyo Publishing Co., Ltd. in 1981) can be cited as examples. For impregnation, batch dyeing machines described in the *Overview of Dyeing Finishing Equipment* (published by Kogyo Publishing Co., Ltd. in 1981) can be cited as examples, and liquid flow dyeing machines, airflow dyeing machines, drum dyeing machines, skein dyeing machines, washing dyeing machines, and package dyeing machines can also be used. For spraying, methods using compressed air to atomize the treatment liquid and spray it out, or air spraying using hydraulic atomization, can be cited as examples.

[0392] The treatment method can be an internal addition treatment by adding a repellent to the pulp before papermaking. The internal addition treatment may include, but is not limited to, one or more steps: a step of adding a repellent to the pulp and mixing it; a step of using a network of a specified shape to dehydrate the pulp composition obtained in this step, causing the pulp composition to accumulate and form a pulp molding intermediate; and a step of using a heated molding die to form and dry the pulp molding intermediate to obtain a pulp molding product. After the treated paper is simply dried at room temperature or high temperature, it can optionally undergo heat treatment depending on the properties of the paper. The heat treatment temperature can be above 150°C, above 180°C, or above 210°C; and can be below 300°C, below 250°C, or below 200°C, particularly 80°C to 180°C. Heat treatment within such a temperature range can exhibit excellent oil and water resistance, etc. The internally added pulp substrate can also be externally treated with a repellent to allow more repellent compounds to adhere to the surface.

[0393] The treatment method can be an external treatment of the pulp substrate after papermaking by applying a sizing agent. Sizing presses with external treatment can be classified according to the coating method as follows. One coating method is the so-called sizing pool type two-roll sizing press, in which paper passes between two rubber rolls, and a coating liquid (sizing liquid) is supplied to the resulting clamping section, forming a coating liquid accumulation section called a sizing pool. The paper passes through this accumulation section, thereby coating both sides of the paper with sizing liquid; other coating methods include weir roll type and metering bar sizing presses that use a surface transfer die to apply the sizing liquid. In the sizing pool type two-roll sizing press, the sizing liquid easily penetrates into the interior of the paper; in the surface transfer die, the sizing liquid components tend to remain on the surface of the paper. Compared to the sizing pool type two-roll sizing press, the coating layer of the surface transfer die tends to remain on the surface of the paper, resulting in a larger coating layer formed on the surface. In this invention, even when using the former type of sizing pool type two-roll sizing press, it is possible to impart properties to the paper. Paper treated in this way, after being simply dried at room temperature or high temperature, can exhibit excellent oil and water resistance, depending on the properties of the paper, by selectively subjecting it to heat treatment at temperatures below 300°C, such as below 200°C, and especially in the range of 80°C to 180°C.

[0394] 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, ordinary liner paper and core paper, neutral pure white roll paper, neutral liner paper, rust-proof liner paper and metal composite 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. Preferred examples of pulp products include food packaging materials and food containers, and particularly pulp molded products for food contact applications.

[0395] The implementation methods have been described above, but it should be understood that various changes in manner and details may be made without departing from the spirit and scope of the claimed protection.

[0396] Example The following examples illustrate the present invention in detail, but the present invention is not limited to these examples.

[0397] <Experimental Methods> The experimental steps are as follows.

[0398] [Particle volume ratio and median particle size (D50)] For liquid-repellent compounds and aqueous dispersions, the volume ratio of particles larger than 100 μm, the volume ratio of particles larger than 10 μm, and the median particle size (D50) are calculated based on the frequency distribution (volume distribution) of the volume reference measured using a laser diffraction / scattering device.

[0399] [Preparation Example 1: Preparation of Decaglycerol Dodecabenone Acid Dispersion] 2 g of decaglycerol dodecyl behenate (degree of polymerization 10, hydroxyl substitution rate: 12 / 12*100 [100%], bio-based content: 100%), 0.2 g of polyoxyethylene trimethyl nonyl ether (HLB: 13), and 17.8 g of water were mixed to obtain precursor A of the water-dispersible scavenger. Precursor A was heated to 80°C and stirred at 7000 rpm for 20 minutes using a homogenizer to obtain the water-dispersible scavenger. The volume fraction of particles larger than 100 μm in the obtained water-dispersible scavenger was 0%, and the median particle size D50 was 19.8 μm.

[0400] [Preparation Example 2: Preparation of Ethylene Distearamide Dispersion] 2 g of N,N'-ethylene bis-stearamide (bio-based content: 97%, melting point: 143℃, particle size: 18 μm), which 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 percentage of particles larger than 100 μm: 3.9%, median volume particle size: 18 μm).

[0401] [Preparation Example 3: Preparation of Ethylene Dihydroxy Stearamide Dispersion] 2 g of N,N'-ethylene-bis-12-hydroxystearamide (bio-based content: 95%, melting point: 145℃, particle size: 17 μm), which was 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 a dispersion composition (volume percentage of particles larger than 100 μm: 5%, median volume particle size: 17 μm).

[0402] [Preparation Example 4: Preparation of Ethylene Dioleamide Dispersion] A water-dispersible composition was obtained by mixing 2 g of N,N'-ethylenedioleamide (bio-based content: 96%, melting point: 116℃, particle size: 24 μm), which had been pulverized using a jet mill, 0.2 g of EO / PO polyalkylene glycol ether (HLB7), and 17.8 g of water. (Volume percentage of particles larger than 100 μm: 0%, median volume diameter: 24 μm) [Preparation Example 5: Preparation of phenylenedimethyldihydroxystearamide dispersion] 2 g of N,N-phenylenedimethyl-bis-12-hydroxystearamide (bio-based content: 83%, particle size: 9 μm), which was 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 percentage of particles larger than 100 μm: 0%, median volume diameter: 9 μm).

[0403] [Preparation Example 6: Preparation of Hexamethylene dihydroxystearamide dispersion] 2 g of N,N'-hexamethylene-bis-12-hydroxystearamide (bio-based content: 85%, melting point: 134℃, particle size: 12 μm), which was 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 percentage of particles larger than 100 μm: 3.5%, median volume particle size: 12 μm).

[0404] [Production of molded pulp products] Pulp molding is performed using an automatic molding machine. A mesh assembly is mounted on a metal mold with multiple suction holes at the bottom, and a metal trough is positioned at the top. A mixture of pulp slurry and a water-dispersible agent (pulp composition) is added to the upper metal trough. From the side of the mold opposite to the side with the mesh assembly, a vacuum pump is used to suction and dehydrate the pulp composition through the mold and the mesh assembly, causing the solid components (pulp, etc.) in the pulp composition to accumulate on the mesh assembly, resulting in a pulp molding intermediate. Next, the obtained pulp molding intermediate is dried from top to bottom under a pressure of 0.05 to 5 MPa using metal male and female molds heated to 60–250°C. This produces a pulp molding product molded into a container shape.

[0405] [Oil resistance test] Pour 100 ml of corn oil at 65°C into the molded pulp. After standing at room temperature for 45 minutes, remove the corn oil from the molded pulp and evaluate the degree of impregnation. Based on the degree of impregnation, set the evaluation values ​​as described below.

[0406] 5: No seepage on the inside.

[0407] 4: The inside is impregnated, but the back side is not.

[0408] 3: There is seepage on the inside and slight seepage on the back side.

[0409] 2: There is seepage on the inside, and the seepage to the back is less than 50% of the area.

[0410] 1: The inner side has seepage, and the seepage towards the back is more than 50% but less than 100% of the area.

[0411] 0: Exudation throughout the back side.

[0412] <Example 1> An aqueous pulp concentrate with a concentration of 0.5 wt% was prepared, containing 25% bagasse pulp and 75% wood pulp relative to the total pulp volume. The decaglycerol dodecyl behenate dispersion of Preparation Example 1 was added to the pulp at a ratio of 3 wt% (solid content) relative to the pulp to prepare a pulp composition. The pulp composition was fed into an automatic molding machine to produce molded pulp articles. An oil resistance test was performed on the prepared molded pulp articles, and the oil resistance score was 4. The results are shown in Table 1.

[0413] <Example 2> An aqueous pulp concentrate with a concentration of 0.5 wt% relative to 100% bagasse pulp was prepared. The decaglycerol dodecyl behenate dispersion of Preparation Example 1 was added to the pulp at a ratio of 3 wt% relative to the pulp as a solid component to prepare a pulp composition. The pulp composition was fed into an automatic molding machine to produce molded pulp articles. An oil resistance test was performed on the prepared molded pulp articles, and the oil resistance score was 4. The results are shown in Table 1.

[0414] <Example 3> In preparing the pulp composition, 0.45 wt% AKD (alkyl ketene dimer) relative to the pulp was added. Otherwise, the same procedure as in Example 1 was followed to produce molded pulp articles. The prepared molded pulp articles were subjected to an oil resistance test, with an oil resistance score of 4. The results are shown in Table 1.

[0415] <Example 4> In preparing the pulp composition, 0.1 wt% rosin sizing agent relative to the pulp was added. Otherwise, the same procedure as in Example 1 was followed to produce pulp molded articles. The prepared pulp molded articles were subjected to an oil resistance test, with an oil resistance score of 4. The results are shown in Table 1.

[0416] <Example 5> Aqueous pulp was prepared using the same procedure as in Example 1. The ethylene bis-stearamide dispersion of Preparation Example 2 was added to the pulp at a ratio of 2 wt% relative to the pulp as solids content to prepare a pulp composition. Pulp molded articles were prepared using the same procedure and subjected to an oil resistance test, with an oil resistance score of 4. The results are shown in Table 1.

[0417] <Example 6> Aqueous pulp was prepared using the same procedure as in Example 1. The ethylene dihydroxy stearamide dispersion of Preparation Example 3 was added to the pulp at a ratio of 3 wt% relative to the pulp as solids content to prepare a pulp composition. The pulp composition was fed into an automatic molding machine to produce molded pulp articles. The molded pulp articles were prepared using the same procedure and subjected to an oil resistance test, with an oil resistance score of 4. The results are shown in Table 1.

[0418] <Example 7> Aqueous pulp was prepared using the same procedure as in Example 1. The ethylene dioleamide dispersion of Preparation Example 4 was added to the pulp at a ratio of 7 wt% relative to the pulp as solids content to prepare a pulp composition. Pulp molded articles were prepared using the same procedure and subjected to an oil resistance test, with an oil resistance score of 4. The results are shown in Table 1.

[0419] <Example 8> Aqueous pulp was prepared using the same procedure as in Example 1. The phenylenedimethyl dihydroxystearamide dispersion of Preparation Example 5 was added to the pulp at a ratio of 2 wt% relative to the pulp as solids content to prepare a pulp composition. Pulp molded articles were prepared using the same procedure and subjected to an oil resistance test, with an oil resistance score of 4. The results are shown in Table 1.

[0420] <Example 9> Aqueous pulp was prepared using the same procedure as in Example 1. The hexamethylene dihydroxystearamide dispersion of Preparation Example 6 was added to the pulp at a ratio of 3 wt% relative to the pulp as solids content to prepare a pulp composition. Pulp molded articles were prepared using the same procedure and subjected to an oil resistance test, with an oil resistance score of 4. The results are shown in Table 1.

[0421] <Comparative Example 1> An aqueous pulp concentrate containing 0.5 wt% of 100% wood pulp was prepared, and pulp molded articles were made in the same manner as in Example 1. The prepared pulp molded articles were subjected to an oil resistance test, with an oil resistance score of 3. The results are shown in Table 1.

[0422] <Comparative Example 2> An aqueous pulp concentrate containing 0.5 wt% of 100% wood pulp was prepared, and pulp molded articles were made in the same manner as in Example 7. The prepared pulp molded articles were subjected to an oil resistance test, with an oil resistance score of 3. The results are shown in Table 1.

[0423] <Comparative Example 3> An aqueous pulp concentrate containing 0.5 wt% of 100% bagasse pulp was prepared. A sugar fatty acid ester dispersion (SEFOSE 1618U, Procter & Gamble Chemicals) was added to the pulp at a ratio of 3 wt% (solid content) relative to the pulp, and a polyamine resin was added at 0.1 wt% (relative to the pulp) as a synergistic agent to prepare the pulp composition. The pulp concentrate was fed into an automatic molding machine to produce molded pulp articles. An oil resistance test was performed, with an oil resistance score of 1. The results are shown in Table 1.

[0424] <Comparative Example 4> An aqueous pulp stock with a concentration of 0.5 wt% (containing 25% bagasse pulp and 75% wood pulp relative to the total pulp volume) was prepared, and the pulp composition was prepared in the same manner as in Comparative Example 3. Molded pulp articles were made and an oil resistance test was performed, with an oil resistance score of 2. The results are shown in Table 1.

[0425] <Comparative Example 5> An aqueous pulp concentrate with a concentration of 0.5 wt% was prepared, containing 25% bagasse pulp and 75% wood pulp relative to the total pulp volume. The pulp concentrate was fed into an automatic molding machine to produce molded pulp products. Oil resistance and water resistance tests were performed on the molded pulp products; both tests scored 0 points.

[0426] <Comparative Example 6> An aqueous pulp concentrate with a concentration of 0.5 wt% relative to the total pulp volume (containing 100% bagasse pulp) was prepared. The pulp concentrate was fed into an automatic molding machine to produce molded pulp products. Oil resistance and water resistance tests were performed on the molded pulp products; both tests scored 0 points.

[0427] The results are summarized in the table below.

[0428] [Table 1] .

Claims

1. A pulp composition, characterized in that, Contains liquid-repellent compounds and pulp substrate. The liquid-repellent compound is a compound containing a monovalent hydrocarbon group with 6 to 40 carbon atoms that may have substituents, and is not a fatty acid ester with a glycosidic bond. The pulp substrate contains bagasse pulp.

2. The pulp composition according to claim 1, characterized in that, The liquid-repellent compound has at least one group selected from -OC(=O)R, -COOR, -NHCOR and -CONHR. In the formula, R is a hydrocarbon group with 6 to 40 carbon atoms that can be monovalent and have substituents.

3. The pulp composition according to claim 1 or 2, characterized in that, The liquid-repellent compound is a compound modified with a hydrocarbon group having 6 to 40 carbon atoms that may have substituents, on an amine, polyol, or polycarboxylic acid.

4. The pulp composition according to any one of claims 1 to 3, characterized in that, The amount of the liquid-repellent compound relative to the pulp substrate is 0.5% to 25% by weight.

5. The pulp composition according to any one of claims 1 to 4, characterized in that, In the pulp substrate, the amount of bagasse pulp is more than 20% by weight and less than 100% by weight.

6. The pulp composition according to any one of claims 1 to 5, characterized in that, The pulp composition contains a dispersant.

7. The pulp composition according to any one of claims 1 to 6, characterized in that, The pulp composition contains paper-grade pharmaceuticals.

8. The pulp composition according to any one of claims 1 to 7, characterized in that, The pulp composition contains a sizing agent.

9. The pulp composition according to any one of claims 1 to 8, characterized in that, The pulp composition contains aluminum sulfate.

10. A pulp molded article obtained by molding the pulp composition according to any one of claims 1 to 9.

11. The pulp molded article as described in claim 10, characterized in that, For food contact use.

12. A method for manufacturing a pulp composition, characterized in that, This includes the process of treating pulp substrates with a repellent agent containing a repellent compound. The liquid-repellent compound is a compound containing a monovalent hydrocarbon group with 6 to 40 carbon atoms that may have substituents, and is not a fatty acid ester with a glycosidic bond. The pulp substrate contains bagasse pulp.

13. The method for manufacturing the pulp composition according to claim 12, characterized in that, The liquid-repellent compound has at least one group selected from -OC(=O)R, -COOR, -NHCOR and -CONHR. In the formula, R is a hydrocarbon group with 6 to 40 carbon atoms that can be monovalent and have substituents.

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