Oil- and water-resistance agent for pulp

Abstract

Provided is a novel oil- and water-resistance agent for pulp, that contains a liquid-repellent compound that is a modified organic acid or a salt thereof. The liquid-repellent compound has a C4-50 monovalent hydrocarbon group, a polar bond, and an acidic group or a salt thereof. The oil- and water-resistance agent can impart oil resistance and / or water resistance to a substrate and particularly a pulp substrate.

Description

Oil and water resistant agent for pulp

[0001] This disclosure relates to repellents, particularly oil and water resistant agents for pulp.

[0002] Patent Document 1 discloses that amide compounds, obtained by modifying bio-based materials with long-chain hydrocarbon groups having 7 to 40 carbon atoms and amide groups, are useful as components of oil-resistant agents.

[0003] WO2022 / 065384A1

[0004] Patent Document 1 does not examine amide compounds that use organic acids as raw materials.

[0005] The purpose of this disclosure is to provide a novel oil and / or water-resistant agent capable of imparting oil resistance and / or water resistance to a substrate, particularly a pulp substrate.

[0006] The disclosure includes the following embodiments: [1] An oil and water resistant agent for pulp comprising a liquid-repellent compound which is a modified organic acid or a salt thereof, wherein the liquid-repellent compound has a monovalent hydrocarbon group having 4 to 50 carbon atoms, a polar bond, and an acidic group or a salt thereof. [2] The oil and water resistant agent according to claim 1, wherein the liquid-repellent compound is a salt of the modified organic acid. [3] The oil and water resistant agent according to claim 1 or 2, wherein the monovalent hydrocarbon group is an alkyl group having 11 or more carbon atoms. [4] The oil and water resistant agent according to any one of claims 1 to 3, wherein the liquid-repellent compound has a structure consisting of an aliphatic hydrocarbon group, the polar bond, and the acidic group or a salt thereof, and the molecular weight of the liquid-repellent compound is 2000 or less. [5] The oil and water resistant agent according to any one of claims 1 to 4, wherein the polar bond is selected from the group consisting of an amide bond, a urethane bond, a urea bond, and an imide bond. [6] The acidic group or a salt thereof is -COOM, -SO ３ M, -OSO ３ M, and -PO ４ M, -P (=O) (OM) ２ An oil- and water-resistant agent according to any one of claims 1 to 5, selected from the group consisting of [wherein M is independently a hydrogen atom or a cation]. [7] The liquid-repellent compound is of the following formula: R １ -A-R ２ (B １ ) (Caution３ -B ２ ) ｎ [In the formula, R １ is a monovalent aliphatic hydrocarbon group having 4 to 50 carbon atoms, A is a polar bond, and R ２ is -CH ２ - or -CH(-) ２ and B １ is an acidic group or a salt thereof, R ３ is a direct bond or a divalent aliphatic hydrocarbon group having 1 to 40 carbon atoms, B ２ is an acidic group or a salt thereof, and n is 0 or 1.] The oil- and water-resistant agent according to any one of items 1 to 6. [8] R １ is an alkyl group having 11 or more carbon atoms, A is selected from the group consisting of an amide bond, a urethane bond, a urea bond, and an imide bond, and B １ and B ２ are each independently selected from the group consisting of -COOM, -SO ３ M, -OSO ３ M, -PO ４ M, and -P(=O)(OM) ２ [wherein M is each independently a hydrogen atom or a cation.] and at least one of B １ and B ２ contains a carboxylic acid group or a salt thereof. The oil- and water-resistant agent according to item 7. [9] The oil- and water-resistant agent according to any one of items 1 to 8, containing a water-soluble polymer.

[10] The oil- and water-resistant agent according to any one of items 1 to 9, which is a water-dispersed composition.

[11] The oil- and water-resistant agent according to any one of items 1 to 10, containing a dispersant.

[12] The oil- and water-resistant agent according to any one of items 1 to 11, containing at least one selected from the group consisting of a yield agent, a sizing agent, a pH adjuster, a filler, and a paper strength enhancer.

[13] A pulp product having the solid content of the oil- and water-resistant agent according to any one of items 1 to 12 adhered thereto.

[14] The pulp product according to item 13, which is a food packaging material or a food container.

[15] A method for producing a pulp product, which comprises treating a pulp substrate with the oil- and water-resistant agent according to any one of items 1 to 12.

[0007] The oil and water resistant agent of this disclosure can suitably impart oil resistance and / or water resistance to a substrate, particularly a pulp substrate.

[0008] <Definition of Terms> As used herein, "n-valent group" means a group having n bonds, that is, a group that forms n bonds. Also, "n-valent organic group" means an n-valent group containing carbon. Such organic groups are not particularly limited, but may be hydrocarbon groups or derivatives thereof. A hydrocarbon group derivative means a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, halogen, etc. at the terminal or molecular chain of a hydrocarbon group.

[0009] As used herein, "hydrocarbon group" means a group containing carbon and hydrogen, obtained by removing a hydrogen atom from a hydrocarbon. Such hydrocarbon groups are not particularly limited, but include C １－２０ Examples of hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The above-mentioned "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. The hydrocarbon group may also contain one or more ring structures. If explicitly stated, the hydrocarbon group may be substituted with one or more substituents.

[0010] In this specification, unless otherwise stated, whether or not the phrases "independently in each occurrence," "independently of each other," "independently of each other," or similar expressions are explicitly stated, when a term (symbol) that may appear multiple times in a chemical structure is defined, the definition shall apply independently to each occurrence.

[0011] The chemical structures described herein should be understood to exclude any chemical structures that would be considered chemically impossible or extremely unstable by those skilled in the art.

[0012] <Repellent Agents (Oil and Water Resistant Agents)> The repellent agents in this disclosure adhere to a substrate (especially a pulp substrate) and can impart liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or antifouling properties to the substrate, and can also function as water resistant agents, oil resistant agents, water repellent agents, oil repellent agents, and / or antifouling agents. The repellent agents in this disclosure are particularly suitable as oil and water resistant agents that impart oil resistance and / or water resistance to a substrate (especially a pulp substrate). The oil and water resistant agents may impart oil resistance to the substrate at least, and may particularly impart both oil resistance and water resistance.

[0013] In one embodiment, by using the repellent agent of this disclosure, oil resistance and / or water resistance can be imparted to a pulp substrate even with a relatively simple formulation (few types of agents and / or small amounts) and low coating amount. By suppressing the amount of agents and coating amount, it is advantageous for producing pulp products that maintain high air permeability, and it is also possible to reduce the environmental impact.

[0014] The repellent agent of this disclosure contains a liquid-repellent compound, which is a modified organic acid or a salt thereof as described below, as an active ingredient. The liquid-repellent compound itself may be used as a repellent agent, or it may be used as a repellent agent in combination with other components.

[0015] The repellent agent in this disclosure does not necessarily have to contain any compound selected from the group consisting of a compound having 8 or more carbon atoms in a fluoroalkyl group, a compound having 8 or more carbon atoms in a perfluoroalkyl group, a compound having 4 or more carbon atoms in a fluoroalkyl group, a compound having 4 or more carbon atoms in a perfluoroalkyl group, a compound having a perfluoroalkyl group, a compound having a fluoroalkyl group, and a compound having a fluorine atom. The repellent agent in this disclosure can impart liquid repellency to a substrate even without containing these fluorine compounds.

[0016] [Characteristics of the repellent agent, etc.] [Particle size, etc.] The volume abundance of particles 100 μm or larger measured by laser diffraction scattering in the repellent agent of this disclosure (a repellent agent which is a dispersion (especially an aqueous dispersion)) may be 0.1% or more, 0.3% or more, 0.5% or more, 1% or more, 1.5% or more, 3% or more, 4% or more, 5% or more, or 10% or more, and may also be 50% or less, 30% or less, 20% or less, 15% or less, 10% or less, 5% or less, 3% or less, or 1.5% or less, preferably 20% or less, and more preferably 5% or less. The method for achieving such a volume abundance of particles within the above range is not limited, but for example, the particles in the raw material and / or dispersion can be finely milled using a pulverizer or homogenizer.

[0017] The volume abundance of particles 10 μm or larger in the repellent agent of this disclosure (a repellent agent which is a dispersion (particularly an aqueous dispersion)) as measured by laser diffraction scattering may be 0.1% or more, 0.3% or more, 0.5% or more, 1% or more, 1.5% or more, 3% or more, 4% or more, 5% or more, or 10% or more, and may also be 50% or less, 30% or less, 20% or less, 15% or less, 10% or less, 5% or less, 3% or less, or 1.5% or less, preferably 30% or less, more preferably 15% or less. The method for achieving such a volume abundance of particles within the above range is not limited, but for example, the particles in the raw material and / or dispersion can be refined using a pulverizer or homogenizer.

[0018] The volume median diameter measured by laser diffraction scattering in the repellent agent of this disclosure (a repellent agent which is a dispersion (particularly an aqueous dispersion)) may be 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.2 μm or more, 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, or 0.6 μm or more, and may also be 10 μm or less, 5 μm or less, 3 μm or less, 1 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, 0.3 μm or less, or 0.2 μm or less, preferably 1 μm or less, and in one embodiment, 0.01 μm or more and 1 μm or less. In this disclosure, volume median diameter refers to the median diameter (D50) in the volume-based particle size distribution measured by laser diffraction scattering.

[0019] The average particle size obtained from scanning electron microscope images of particles obtained by removing the liquid medium from an aqueous dispersion of a repellent agent (e.g., an oil- and water-resistant agent for pulp) at room temperature by natural drying is 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.2 μm or more, 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, or 0.6 μm or more, and may also be 10 μm or less, 5 μm or less, 3 μm or less, 1 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, 0.3 μm or less, or 0.2 μm or less, preferably 1 μm or less. To achieve a particle size within the above range, for example, the particles in the raw material and / or dispersion can be finely ground using a pulverizer or homogenizer. Room temperature is defined as 20°C to 30°C, and especially 25°C.

[0020] [Ionic Charge Density] The ionic charge density in the repellent of this disclosure may be -1000 μeq / g or more, -800 μeq / g or more, -600 μeq / g or more, -500 μeq / g or more, -400 μeq / g or more, -250 μeq / g or more, -100 μeq / g or more, -50 μeq / g or more, -25 μeq / g or more, 0 μeq / g or more, 1 μeq / g or more, 25 μeq / g or more, 50 μeq / g or more, 100 μeq / g or more, or 200 μeq / g or more, preferably -600 μeq / g or more, for example, -400 μeq / g or more, -200 μeq / g or more, or -50 μeq / g or more, and also 5000 μeq / g or less. The amount may be 2500 μeq / g or less, 1000 μeq / g or less, 750 μeq / g or less, 600 μeq / g or less, 500 μeq / g or less, 400 μeq / g or less, 350 μeq / g or less, 300 μeq / g or less, 200 μeq / g or less, 100 μeq / g or less, or 50 μeq / g or less, preferably 1000 μeq / g or less, more preferably 500 μeq / g or less, for example 300 μeq / g or less, particularly 100 μeq / g or less, and in a preferred embodiment, it may be -1500 μeq / g or more and 1500 μeq / g or less, particularly -1500 μeq / g or more and 0 μeq / g or less.

[0021] The anion demand of a sample solution containing 0.1 g / L solids is measured using a 1 / 1000 N potassium polyvinylsulfonate solution with a particle charge meter (BTG MUTEK PCD-06), and the ion charge density (cation charge density) is calculated from the following formula (1). Alternatively, the cation demand is measured similarly using a polydiallyldimethylammonium chloride solution instead of potassium polyvinylsulfonate, and the ion charge density (anion charge density) is calculated from the following formula (1). Ion charge density (μeq / g) = A / B (1) A: Cation demand or anion demand (μeq / L) B: Sample solution concentration (g / L)

[0022] [pH] The pH of the repellent may be 0.1 or higher, 0.3 or higher, 0.5 or higher, 1 or higher, 2 or higher, 3 or higher, 4 or higher, 5 or higher, 6 or higher, 7 or higher, 8 or higher, or 9 or higher, and may also be 13 or lower, 12 or lower, 11 or lower, 10 or lower, 9.5 or lower, 8.5 or lower, 7.5 or lower, 6.5 or lower, 5.5 or lower, 4.5 or lower, 3.5 or lower, 2.5 or lower, or 1.5 or lower. In one embodiment containing a salt-form liquid-repellent compound, the pH of the repellent may be 0.1 to 13, and in particular, 7 to 13, for example, 7 to 11, or 8 to 10. The pH of a repellent obtained by replacing the acidic groups in the repellent with a salt, such as an alkali metal salt or an alkaline earth metal salt, particularly a sodium salt or a potassium salt, may be 0.1 to 13, and in particular may be 5 or higher, 6 or higher, 7 or higher, 8 or higher, or 9 or higher, and may also be 11 or lower, 10 or lower, or 9 or lower, and in one embodiment it may be 7 to 11, for example 8 to 10.

[0023] [Liquid-repellent compounds (modified organic acids or salts thereof)] The repellents in this disclosure include liquid-repellent compounds which are modified organic acids or salts thereof. The liquid-repellent compounds in this disclosure adhere to a substrate (especially a pulp substrate) and can impart liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or antifouling properties to the substrate, and can particularly suitably impart oil resistance.

[0024] [Properties, etc.] The properties, etc. that liquid-repellent compounds may possess are shown below.

[0025] The HD (n-hexadecane) contact angle of the liquid-repellent compound may be 10° or more, 20° or more, 25° or more, 30° or more, 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 60° or more, or 65° or more, preferably 25° or more, more preferably 30° or more, and may also be 100° or less, 90° or less, or 75° or less. By having an HD contact angle of the liquid-repellent compound above the lower limit, good liquid repellency (especially oil repellency) can be imparted to the substrate. The HD contact angle is the static contact angle of the liquid-repellent compound with respect to the spin-coated film, and is obtained by dropping 2 μL of HD onto the spin-coated film and measuring the contact angle 1 second after the drop.

[0026] The water contact angle of the liquid-repellent compound is 35° or higher, 40° or higher, 45° or higher, 50° or higher, 55° or higher, 65° or higher, 75° or higher, 85° or higher, 90° or higher, or 100° or higher, and may also be 160° or lower, 140° or lower, 130° or lower, 120° or lower, 110° or lower, 100° or lower, or 90° or lower. By having a water contact angle of the liquid-repellent compound above the lower limit, good liquid repellency (especially water repellency) can be imparted to the substrate. The water contact angle is the static contact angle of the liquid-repellent compound with respect to the spin-coated film, and is obtained by dropping 2 μL of water onto the spin-coated film and measuring the contact angle 1 second after the drop.

[0027] The melting point of the liquid-repellent compound may be 30°C or higher, 40°C or higher, 60°C or higher, 80°C or higher, 100°C or higher, or 120°C or higher, preferably 40°C or higher, and may also be 250°C or lower, 225°C or lower, 200°C or lower, 150°C or lower, 130°C or lower, 120°C or lower, 110°C or lower, 100°C or lower, 80°C or lower, or 50°C or lower. The above melting point may be the melting point of the liquid-repellent compound in a form other than a salt.

[0028] [Structure, etc.] The liquid-repellent compound in this disclosure is a modified organic acid or a salt thereof, having a monovalent hydrocarbon group with 4 to 50 carbon atoms, a polar bond, and an acidic group or a salt thereof.

[0029] Modified organic acids are organic compounds having an acidic group, which may be aliphatic or aromatic, and are particularly aliphatic.

[0030] The liquid-repellent compound does not necessarily have to contain any of the group selected from the group consisting of fluoroalkyl groups having 8 or more carbon atoms, perfluoroalkyl groups having 8 or more carbon atoms, fluoroalkyl groups having 4 or more carbon atoms, perfluoroalkyl groups having 4 or more carbon atoms, perfluoroalkyl groups, fluoroalkyl groups, and fluorine atoms. Even if the liquid-repellent compound does not contain these fluorine-containing groups, it can still impart liquid repellency to the substrate.

[0031] (Molecular weight) The molecular weight of the liquid-repellent compound may be 150 or more, 250 or more, 350 or more, 450 or more, 550 or more, 650 or more, 750 or more, or 850 or more, and may be 5000 or less, 4000 or less, 3000 or less, 2000 or less, 1500 or less, 1000 or less, 900 or less, 800 or less, 700 or less, 600 or less, 500 or less, 400 or less, 300 or less, or 200 or less, and is particularly 2000 or less, and in one embodiment it is 150 or more and 2000 or less.

[0032] (Monovalent hydrocarbon group having 4 to 50 carbon atoms) The liquid-repellent compounds in this disclosure have a monovalent hydrocarbon group having 4 to 50 carbon atoms. The monovalent hydrocarbon group having 4 to 50 carbon atoms may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and may be an aliphatic hydrocarbon group in particular, such as a saturated or unsaturated aliphatic hydrocarbon group (alkyl group, alkenyl group, etc., especially alkyl group). The hydrocarbon group may be linear, branched, or cyclic.

[0033] In a monovalent hydrocarbon group having 4 to 50 carbon atoms, the number of carbon atoms in the hydrocarbon group may be 4 or more, 6 or more, 8 or more, 10 or more, 11 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, 11 or more, 12 or more, or 16 or more, particularly 11 or more, and may also be 50 or less, 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 40 or less, 30 or less, 25 or less, or 20 or less, and in one embodiment, 6 to 40, 8 to 36, 11 to 30, or 11 to 24.

[0034] The number of monovalent hydrocarbon groups having 4 to 50 carbon atoms in the liquid-repellent compound may be 1 or more, 2 or more, 3 or more, 5 or more, or 8 or less, 6 or less, 4 or less, 2 or less, and in one embodiment, it may be 1 to 3, for example, 1.

[0035] (Polar Bonds) The liquid-repellent compounds in this disclosure have polar bonds. The polar bonds may have an amide structure. Here, an amide structure means a structure (NHCO) that can be formed by the dehydration condensation of an oxo acid and an amine, and examples of bonds having such an amide structure include amide bonds, urethane bonds, urea bonds, or imide bonds.

[0036] The polar bond may be selected from amide bonds, urethane bonds, urea bonds, and imide bonds, and may be particularly amide bonds, urethane bonds, or urea bonds. Specific examples of amide bonds, urethane bonds, urea bonds, and imide bonds may include carboxylic acid amide groups, carboxylic acid urethane groups, carboxylic acid urea groups, carboxylic acid imide groups, thioamide groups, thiourethane groups, thiourea groups, thioimide groups, sulfonamide groups, sulfonurea groups, sulfonurethane groups, or sulfonimide groups. For example, the liquid-repellent compound may be -C(=O)-NH-, -O-C(=O)-NH-, -NH-C(=O)-, -NH-C(=O)-NH-, or -SO ２ It may contain NH-.

[0037] A polar bond may be bonded to a monovalent hydrocarbon group having 4 to 50 carbon atoms, for example, the following structures may be formed: -NHC(=O)-R -C(=O)NH-R -NHC(=O)O-R -OC(=O)NH-R -NHC(=O)NH-R -NH-S(=O) ２ -R, and -S (=O) ２ -NH-R [wherein each R is independently a monovalent hydrocarbon group having 4 to 50 carbon atoms.]

[0038] The number of polar bonds in the liquid-repellent compound may be 1 or more, 2 or more, 3 or more, or 5 or more, and may also be 8 or less, 6 or less, 4 or less, or 2 or less. In one embodiment, it may be 1 or more and 3 or less, for example, 1.

[0039] At least one polar bond may connect a hydrocarbon group to another hydrocarbon group (particularly an aliphatic hydrocarbon group), that is, the liquid-repellent compound may have the structure of hydrocarbon group-polar bond-hydrocarbon group. Here, the number of carbon atoms in each hydrocarbon group may be independently 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 8 or more, 10 or more, or 11 or more, and may be 50 or less, 40 or less, 30 or less, 20 or less, 10 or less, 5 or less, or 3 or less. Here, each hydrocarbon group may independently be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, particularly an aliphatic hydrocarbon group. Furthermore, each hydrocarbon group may independently be a 1- to 3-valent group, and in particular, the group at one end of the polar bond may be the aforementioned "monovalent hydrocarbon group with 4 to 50 carbon atoms".

[0040] (Acidic Groups or Salts thereof) The liquid-repellent compounds in this disclosure have acidic groups or salts thereof. The acidic groups may be oxoacid groups, particularly carbon, sulfur, or phosphorus oxoacid groups or salts thereof. Examples of acidic groups or salts thereof include -COOM, -SO ３ M, -OSO ３ M, -PO ４ M, and -P (=O) (OM) ２ Examples include [wherein M is independently a hydrogen atom or a cation]. The acidic group or its salt is preferably a carboxylic acid or its salt, and the liquid-repellent compound preferably contains one or more carboxylic acid groups or its salts. The valency of the acidic group or its salt is monovalent or polyvalent, and may be 1 to 3 valencies, for example, 1 or 2 valencies, and especially 1 valency.

[0041] In carboxylic acids or their salts, the cation is not particularly limited. Examples of cations include various metal ions (e.g., alkali metal salts), ammonium ions, and organic ammonium cations. The valency of the cation is monovalent or polyvalent, and may be 1 to 3 valencies, for example, 1 or 2 valencies, and especially 1 valency.

[0042] The liquid-repellent compound in this disclosure may be a salt of the modified organic acid. In the dispersion medium, the modified organic acid or its salt may be in equilibrium between the acid structure and the salt structure (ionic structure), and the proportion of the modified organic acid or its salt that is in salt (ionic structure) form may be 10 mol% or more, 30 mol% or more, 50 mol% or more, 70 mol% or more, or 90 mol% or more, and may also be 100 mol% or less, 80 mol% or less, 60 mol% or less, 40 mol% or less, or 20 mol% or less. This proportion can be adjusted by changing the pH.

[0043] The number of acidic groups or their salts in the liquid-repellent compound may be 1 or more, 2 or more, 3 or more, or 5 or more, and may also be 8 or less, 6 or less, 4 or less, or 2 or less. In one embodiment, it may be 1 to 4 or less, 1 to 3 or less, or 1 to 2 or less.

[0044] (Examples of structures of liquid-repellent compounds) Liquid-repellent compounds may have a structure consisting of an aliphatic hydrocarbon group, a polar bond, and an acidic group or a salt thereof. Here, there may be one or more aliphatic hydrocarbon groups, polar bonds, acidic groups or salts thereof, and the aliphatic hydrocarbon group includes a monovalent aliphatic hydrocarbon group having 4 to 50 carbon atoms.

[0045] The aforementioned liquid-repellent compound is of the following formula: R １ -A-R ２ (B １ ) (Caution ３ -B ２ ) ｎ [In the formula, R １ A is a monovalent aliphatic hydrocarbon group having 4 to 50 carbon atoms, A is a polar bond, and R ２ ha-CH ２ - or -CH(-) ２ B １ R is an acidic group or a salt thereof. ３ B is a directly bonded or divalent aliphatic hydrocarbon group having 1 to 40 carbon atoms. ２ The compound may be represented by [where n is an acidic group or a salt thereof, and n is 0 or 1].

[0046] R １This is a monovalent aliphatic hydrocarbon group having 4 to 50 carbon atoms; for details, please refer to the above explanation of (monovalent hydrocarbon group having 4 to 50 carbon atoms).

[0047] A is a polar bond; for details, please refer to the explanation of (polar bonds) above.

[0048] R ２ ha-CH ２ - or -CH(-) ２ That is the case.

[0049] R ３ This is a directly bonded or divalent aliphatic hydrocarbon group having 1 to 40 carbon atoms. The aliphatic hydrocarbon group may be saturated or unsaturated. The aliphatic hydrocarbon group may be branched, cyclic, or linear.

[0050] R ３ The number of carbon atoms may be 0, 1 or more, 2 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, and may also be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, 5 or less, 3 or less, 2 or less, or 1 or less.

[0051] B １ and B ２ Each of these is independently an acidic group or a salt thereof; for details, refer to (acidic group or salt thereof). B １ and B ２ At least one of them may be a carboxylic acid group or a salt thereof.

[0052] n is either 0 or 1.

[0053] (Specific examples of liquid-repellent compounds) Specific examples of liquid-repellent compounds include, as acidic group-containing compounds, sarcosine derivatives such as capryloyl sarcosine, lauroyl sarcosine, myristoyl sarcosine, palmitoyl sarcosine, and coconut oil fatty acid sarcosine; glutamic acid derivatives such as capryloyl glutamic acid, lauroyl glutamic acid, myristoyl glutamic acid, palmitoyl glutamic acid, stearoyl glutamic acid, coconut oil fatty acid acyl glutamic acid, cocoyl glutamic acid, acyl glutamic acid, and dilauroyl glutamic acid; glycine derivatives such as lauroyl glycine, myristoyl glycine, palmitoyl glycine, palmitoyl methylglycine, coconut oil fatty acid acyl glycine, and cocoyl glycine; lauryl methylalanine, myristoyl methylalanine, cocoyl alanine, coconut Examples include alanine derivatives such as methylalanine fatty acid; lysine derivatives such as lauroyl lysine, myristoyl lysine, palmitoyl lysine, stearoyl lysine, oleyl lysine, and acylated lysine; aspartic acid derivatives such as lauroyl aspartic acid, myristoyl aspartic acid, palmitoyl aspartic acid, and stearoyl aspartic acid; taurine derivatives such as lauroyl taurine, lauroyl methyl taurine, myristoyl taurine, myristoyl methyl taurine, palmitoyl taurine, palmitoyl methyl taurine, stearoyl taurine, and stearoyl methyl taurine; and proline derivatives such as lauroyl proline, myristoyl proline, and palmitoyl proline, which are derivatives of amino acids having hydrocarbon groups.

[0054] The compounds in salt form may be the above salts (e.g., alkali metal salts), such as sarcosine derivative salts like potassium capryloyl sarcosinate, sodium capryloyl sarcosinate, potassium lauroyl sarcosinate, sodium lauroyl sarcosinate, potassium myristoyl sarcosinate, sodium myristoyl sarcosinate, potassium palmitoyl sarcosinate, sodium palmitoyl sarcosinate, potassium coconut oil fatty acid sarcosinate, sodium coconut oil fatty acid sarcosinate; potassium capryloyl glutamate, sodium capryloyl glutamate Thorium, potassium lauroyl glutamate, sodium lauroyl glutamate, potassium myristoyl glutamate, sodium myristoyl glutamate, sodium palmitoyl glutamate, magnesium palmitoyl glutamate, potassium stearoyl glutamate, sodium stearoyl glutamate, potassium coconut oil fatty acid acyl glutamate, sodium coconut oil fatty acid acyl glutamate, potassium cocoyl glutamate, sodium cocoyl glutamate, potassium acyl glutamate, acyl glutamate Glutamic acid derivative salts such as sodium phosphate, sodium dilauroyl glutamate lysine, and sodium polyglutamate; glycine derivative salts such as potassium lauroyl glycinate, sodium lauroyl glycinate, potassium myristoyl glycinate, sodium myristoyl glycinate, sodium palmitoyl glycinate, sodium palmitoyl methylglycinate, potassium coconut oil fatty acid acylglycinate, sodium coconut oil fatty acid acylglycinate, potassium cocoyl glycinate, and sodium cocoyl glycinate; alanine derivative salts such as potassium lauroyl methylalanine, sodium lauryl methylalanine, sodium myristoyl methylalanine, sodium cocoyl alanine, and sodium coconut oil fatty acid methylalanine; aspartic acid derivative salts such as potassium lauroyl aspartate, sodium lauroyl aspartate, potassium myristoyl aspartate, sodium myristoyl aspartate, potassium palmitoyl aspartate, sodium palmitoyl aspartate, potassium stearoyl aspartate, and sodium stearoyl aspartate;Examples include taurine derivative salts such as sodium lauroyl taurate, potassium lauroyl taurate, sodium lauroyl methyl taurate, potassium myristoyl taurate, sodium myristoyl taurate, sodium myristoyl methyl taurate, potassium palmitoyl taurate, sodium palmitoyl taurate, potassium palmitoyl methyl taurate, sodium palmitoyl methyl taurate, potassium stearoyl taurate, sodium stearoyl taurate, and sodium stearoyl methyl taurate; and amino acid derivative salts having hydrocarbon groups such as sodium lauroyl proline, sodium myristoyl proline, and sodium palmitoyl proline. The liquid-repellent compound may be an N-acyl derivative of an amino acid or a salt thereof.

[0055] [Method for Producing Liquid-Repellent Compounds] A modified organic acid, which is a liquid-repellent compound, can be obtained, for example, by reacting a predetermined functional group of a raw material organic acid with a predetermined modifier while leaving the acidic group of the raw material organic acid intact. The raw material organic acid may be an amino acid (a compound having both an amino acid and a carboxyl group), and may be α-amino acids, β-amino acids, γ-amino acids, δ-amino acids, etc., or may be an amino acid that makes up a protein, for example, glycine, alanine, valine, leucine, isoleucine, serine, threonine, proline, etc. The modifier may be a compound having a hydrocarbon group (particularly the "monovalent hydrocarbon group having 4 to 50 carbon atoms" mentioned above) and a reactive group (for example, a carboxylic acid, acid chloride, acid anhydride, isocyanate, amino group, etc.). For example, it can be obtained by reacting a functional group such as an amino group or hydroxyl group of an amino acid (e.g., an amino group) with an aliphatic hydrocarbon group such as a lauryl group or a behenyl group, and a modifier having a reactive group that is reactive with the functional group (e.g., a carboxylic acid, acid chloride, acid anhydride, isocyanate, etc.). A person skilled in the art can appropriately design the reaction conditions depending on the desired product, such as by using a catalyst (e.g., an acid catalyst or a base catalyst) or a condensing agent.

[0056] [Amount of liquid-repellent compound] The amount of liquid-repellent compound may be 0.01% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, or 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, or 3% by weight or less. The liquid-repellent compound may be used alone as a repellent.

[0057] [Water-soluble polymers] The water- and oil-repellent agents in this disclosure may include water-soluble polymers.

[0058] The water solubility of the water-soluble polymer at 25°C may be 0.1 g / l or more, 0.5 g / l or more, 1 g / l or more, 3 g / l or more, 5 g / l or more, or 10 g / l or more, and preferably 3 g / l or more.

[0059] The weight-average molecular weight of the water-soluble polymer may be 1,000 or more, 3,000 or more, 5,000 or more, 10,000 or more, 30,000 or more, 100,000 or more, 300,000 or more, or 500,000 or more, and may also be 1,000,000 or less, 750,000 or less, 500,000 or less, 3,000,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, 5,000 or less, or 3,000 or less.

[0060] The water-soluble polymer may be hydrophobically modified. A hydrophobically modified water-soluble polymer may mean a compound modified with, for example, one or more, two or more, three or more, five or more, ten or more, thirty or more, or fifty or more hydrophobic functional groups (e.g., hydrocarbon groups with six or more, ten or more, twelve or more, twelve or more, or fifty or more carbon atoms).

[0061] Examples of water-soluble polymers include polysaccharides, synthetic polyols, polyamines, polycarboxylic acids, polyamides, and polyethers, with polysaccharides or synthetic polyols being preferred.

[0062] The water-soluble polymer is preferably a polyol, and may be a polysaccharide or a synthetic polyol. The number of hydroxyl groups in the polyol may be 10 or more, 15 or more, 30 or more, 50 or more, or 100 or more, and may also be 3000 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less.

[0063] Polysaccharides may be acidic polysaccharides, neutral sugars, and / or basic sugars, but are preferably neutral. Acidic polysaccharides are generally polysaccharides having a carboxyl group (-COOH), etc. Specific examples of acidic polysaccharides are carrageenan, pectin, gum arabic, xanthan gum, gellan gum, agar, and tragacanth gum. Neutral polysaccharides are polysaccharides that are electrically neutral. Specific examples of neutral polysaccharides are tamarind seed gum, guar gum, locust bean gum, starch, and pullulan. Basic polysaccharides are polysaccharides having an amino group (-NH). ２ These are polysaccharides containing ) etc. A specific example of a basic polysaccharide is chitosan. Specific examples of polysaccharides include starch, xanthan gum, karaya gum, welan gum, guar gum, pectin, tamarind gum, carrageenan, chitosan, gum arabic, locust bean gum, cellulose, alginic acid, agar, dextran, and pullulan.

[0064] As the polysaccharide, starch is preferred. The starch may be unmodified starch or modified starch. The starch may be modified starch that has undergone at least one modification, such as esterification modification, hydrophobization modification, etherification modification, oxidation modification, alkali modification, enzyme modification, and bleach modification. Examples of modified starches include acetylated adipic acid crosslinked starch, acetylated oxidized starch, acetylated phosphate crosslinked starch, alkenyl succinate esterified starch, acetate starch, oxidized starch, hydroxyalkylated starch (alkyl group having 2 to 40 or 2 to 10 carbon atoms, particularly 2 or 3 carbon atoms), hydroxyalkylated phosphate crosslinked starch (alkyl group having 2 to 40 or 2 to 10 carbon atoms, particularly 2 or 3 carbon atoms), phosphate crosslinked starch, phosphorylated starch, phosphate monoesterified phosphate crosslinked starch, acid-modified starch, alkali-treated starch, enzyme-treated starch, bleach-treated starch, and cationized starch (quaternary ammonium starch). Dextrin, which is starch that has been reduced in molecular weight by chemical or enzymatic methods, can also be mentioned. The starch may be pregelatinized starch. Pregelatinized starch is starch in which the hydrogen bonds between sugar chains have been broken, and the spaces between sugar chains have become free.

[0065] Synthetic polyols are synthetic polyols having a plurality of hydroxyl groups (for example, 10 or more, 50 or more, 100 or more, or 500 or more) in their molecule. Preferably, examples include polyglycerin, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymer, hydroxypropyl (meth)acrylate polymer, hydroxybutyl (meth)acrylate polymer, polyvinyl alcohol (saponification degree of 80% or more, 90% or more, or 95% or more, etc.), and polyvinyl alcohol may be particularly preferred.

[0066] Specific examples of water-soluble polymers include polysaccharides such as starch, pullulan, amylose, cellulose, cellulose derivatives, carrageenan, guar gum, chitin, chitosan, locust bean gum, kappa-carrageenan, iota-carrageenan, isomaltodextrin, gellan gum, and tamarind seed gum; synthetic polyols such as polyglycerin, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymer, hydroxypropyl (meth)acrylate polymer, hydroxybutyl (meth)acrylate polymer, and polyvinyl alcohol; and polyethylene. Examples include polyamines such as imines, polyvinylamines, and polyallylamines; polyamides such as polyvinylpyrrolidone, polyacrylamide, poly(N,N-dimethylacrylamide), poly(N-vinylacetamide), poly-N-isopropylacrylamide, polyoxazolines (e.g., poly(2-methyl-2-oxazoline), poly(2-ethyl-2-oxazoline), poly(2-propyl-2-oxazoline)), and polyamideimides; and polyethers such as polyethylene glycol, polypropylene glycol, and polyvinyl methyl ether.

[0067] [Amount of water-soluble polymer] The amount of water-soluble polymer may be 10 parts by weight or more, 30 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, 750 parts by weight or more, 1000 parts by weight or more, 1500 parts by weight or more, or 2000 parts by weight or more, preferably 100 parts by weight or more, and may also be 5000 parts by weight or less, 4500 parts by weight or less, 4000 parts by weight or less, 3500 parts by weight or less, 3000 parts by weight or less, 2500 parts by weight or less, 2000 parts by weight or less, 1500 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, or 100 parts by weight or less, preferably 900 parts by weight or less.

[0068] [Other Liquid-Repellent Compounds] The liquid-repellent agent in this disclosure may include other liquid-repellent compounds in addition to modified organic acids or their salts. Other liquid-repellent compounds can be liquid-repellent compounds that are active ingredients of known liquid-repellent agents, such as non-fluorine liquid-repellent compounds. Examples of liquid-repellent compounds include, but are not limited to, acrylic polymers described in WO / 2020 / 054856, WO / 2017 / 159754, WO / 2020 / 162547, etc., polyurethanes described in JP 2016-524628, JP 2017-533976, JP 2017-504730, WO / 2021 / 132170, WO / 2021 / 132172, etc., natural product modifiers described in WO / 2022 / 065382, and WO / 2022 / 065385, etc., polyesters, polylactic acid, silicones, etc.

[0069] [Amount of other liquid-repellent compounds] The amount of other liquid-repellent compounds may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, per 100 parts by weight of the liquid-repellent compound, or 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less.

[0070] [Dispersant] The repellent agent in this disclosure may include a dispersant. In one embodiment of this disclosure, the liquid-repellent compound of this disclosure has excellent dispersibility (particularly water dispersibility), so that good oil resistance and / or water resistance can be imparted to the pulp substrate even with reduced use of a dispersant (surfactant) or without use of a dispersant (surfactant). 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.

[0071] The dispersant may be either an organic dispersant or an inorganic dispersant, or a combination of both.

[0072] Organic dispersants may be used as dispersants. Organic dispersants can be classified into nonionic dispersants, anionic dispersants, cationic dispersants, and amphoteric dispersants, and the term "organic dispersant" may refer to surfactants.

[0073] The dispersant may be fluorine-free.

[0074] [Nonionic Dispersant] The dispersant may contain a nonionic dispersant. The nonionic dispersant may be a nonionic surfactant.

[0075] The nonionic dispersant may be of low molecular weight or high molecular weight. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 100000 or less, 10000 or less, 7500 or less, 5000 or less, 25000 or less, 750 or less, or 250 or less.

[0076] Examples of nonionic dispersants include ethers, esters, ester ethers, alkanolamides, polyols, and amine oxides.

[0077] Examples of ethers are compounds having an oxyalkylene group (preferably a polyoxyethylene group).

[0078] Examples of esters are esters of alcohols and fatty acids. Examples of alcohols are alcohols with 1 to 50 carbon atoms (especially 10 to 30 carbon atoms) with 1 to 30 valencies (especially 2 to 10 valencies) (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids with 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

[0079] Examples of ester ethers are compounds obtained by adding an alkylene oxide (especially ethylene oxide) to an ester of an alcohol and a fatty acid. Examples of alcohols are alcohols with 1 to 50 carbon atoms (especially 3 to 30 carbon atoms) with a novalence of 1 to 30 (especially 2 to 10) (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids with 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

[0080] Examples of alkanolamides are formed from fatty acids and alkanolamines. Alkanolamides may be monoalkanolamides or dialkanolaminos. Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. Alkanolamines may be alkanols having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0081] The polyol may be a divalent to pentavalent alcohol having 10 to 30 carbon atoms. The amine oxide may be an oxide of an amine (secondary amine or preferably tertiary amine) (for example, having 5 to 50 carbon atoms).

[0082] The nonionic dispersant is preferably a nonionic dispersant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms in the alkylene group of the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic dispersant is generally preferably 2 to 100.

[0083] The nonionic dispersant is selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyols, and amine oxides, and is preferably a nonionic dispersant having an oxyalkylene group.

[0084] The nonionic dispersant may be an alkylene oxide adduct of linear and / or branched aliphatic (saturated and / or unsaturated) groups, a polyalkylene glycol ester of linear and / or branched fatty acids (saturated and / or unsaturated), a sorbitan ester of linear and / or branched fatty acids (saturated and / or unsaturated), a glycerol ester of linear and / or branched fatty acids (saturated and / or unsaturated), a polyglycerol ester of linear and / or branched fatty acids (saturated and / or unsaturated), a sucrose ester of linear and / or branched fatty acids (saturated and / or unsaturated), a polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of acetylene glycol, and the like. Among these, those in which the alkylene oxide addition portion and the polyalkylene glycol portion are structured as polyoxyethylene (POE), polyoxypropylene (POP), or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred. Furthermore, the nonionic dispersant does not need to contain aromatic groups.

[0085] Nonionic dispersants are given by formula: R １ O-(CH ２ CH ２ O) ｐ - (R ２ O) ｑ -R ３ [In the formula, R １ R is an alkyl group having 1 to 22 carbon atoms, or an alkenyl group or acyl group having 2 to 22 carbon atoms. ２ Each of them is independently identical or distinct, an alkylene group having 3 or more carbon atoms (for example, 3 to 10), R ３ The compound may be represented by [where p is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms, p is a number of 2 or more, and q is a number of 0 or 1 or more].

[0086] R １ The carbon atoms have 8 to 20 carbon atoms, and are more preferably 10 to 18 carbon atoms. １Preferred specific examples include the octyl group, nonyl group, trimethylnonyl group, lauryl group, tridecyl group, oleyl group, and stearyl group. ２ Examples include propylene groups and butylene groups. In nonionic dispersants, p may be a number of 3 or more (e.g., 5 to 200). q may be a number of 2 or more (e.g., 5 to 200). That is, -(R ２ O) ｑ - may form a polyoxyalkylene chain. The nonionic dispersant may be a polyoxyethylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) in the center. Examples of hydrophobic oxyalkylene chains include oxypropylene chains, oxybutylene chains, and styrene chains, but oxypropylene chains are preferred among them.

[0087] Specific examples of nonionic dispersants include ethylene oxide and hexylphenol, isooctatylphenol, hexadecanol, oleic acid, and alkanes (C). １２ -C １６ ) Thiol, sorbitan monofatty acid (C ７ -C １９ ) or alkyl (C １２ -C １８ This includes condensation products with amines, sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, lecithin derivatives, etc. Examples of nonionic dispersants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene polyoxybutylene alkyl ethers, polyoxyethylene polyoxypropylene glycol, polyethyleneimine ethoxylate, etc.

[0088] The proportion of polyoxyethylene blocks can be 5 to 80% by weight, for example 30 to 75% by weight, and particularly 40 to 70% by weight, relative to the molecular weight of the nonionic dispersant (copolymer). The average molecular weight of the nonionic dispersant is generally 300 to 5,000, for example 500 to 3,000. The nonionic dispersant may be a single type or a mixture of two or more types. The nonionic dispersant may be a mixture of a compound with an HLB (hydrophilic-hydrophobic balance) of less than 15 (particularly 5 or less) and a compound with an HLB of 15 or more. Specifically, it is preferable to select from polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene, polyoxypropylene with HLBs of 1 to 18, or sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene glycerin fatty acid esters, and polyoxyethylene sorbitan fatty acid esters with HLB values ​​of less than 7.

[0089] [Cationic Dispersant] The dispersant may contain a cationic dispersant. The cationic dispersant may be a cationic surfactant. The cationic dispersant may be a compound that does not have an amide group.

[0090] The cationic dispersant may be of low molecular weight (for example, molecular weight of 2000 or less, particularly 10000 or less) or high molecular weight (for example, molecular weight of 2000 or more). The molecular weight of the cationic dispersant may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 1000000 or less, 750000 or less, 500000 or less, 250000 or less, 100000 or less, 50000 or less, 100000 or less, 7500 or less, 50000 or less, 250000 or less, 750 or less, or 250 or less.

[0091] The cationic dispersant may be aliphatic or aromatic, and examples thereof include ammonium salts (e.g., quaternary ammonium salts). The cationic dispersant may be an ethylene oxide-added type ammonium salt. Specifically, amine salt type dispersants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline; quaternary ammonium salt type dispersants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzalkonium chloride, benzethonium chloride, etc.; polymeric cationic dispersants such as polyquaternium-1 to 47, etc. Examples of the cationic dispersant include alkylamine salts, quaternary ammonium salts, etc.

[0092] The low molecular weight cationic dispersant is R ２１ -N ＋ (-R ２２ )(-R ２３ )(-R ２４ )X － [In the formula, R ２１ , R ２２ , R ２３ and R ２４ are hydrogen or a hydrocarbon group having 1 to 40 carbon atoms, and X is an anionic group. ] It may be a compound represented by. Specific examples of R ２１ , R ２２ , R ２３ and -R ２４ are an alkyl group (e.g., methyl group, butyl group, stearyl group, palmityl group), an aromatic group (e.g., benzyl group, phenyl group), etc. Specific examples of X are halogen (e.g., chlorine), acid (e.g., hydrochloric acid, acetic acid). Examples of the cationic dispersant include monoalkyltrimethylammonium salts (alkyl having 4 to 40 carbon atoms), benzalkonium chloride, etc.

[0093] Specifically, the low molecular weight cationic dispersant has the formula: R １ ｐ -N ＋ R ２ ｑ X － [In the formula, R １ is C12 or more (e.g., C１２ ~C ５０ ) is a linear and / or branched aliphatic (saturated and / or unsaturated) group, R ２ (CH) is an H or C1-C4 alkyl group, a benzyl group, a polyoxyethylene group (number of oxyethylene groups e.g., 1 (especially 2, particularly 3) to 50) ３ , C ２ H ５ (particularly preferred) where X is a halogen atom (e.g., chlorine), or C １ ~C ４ fatty acid salts of, or C １ ~C ４ It is a sulfonate of , where p is 1 or 2, q is 2 or 3, and p + q = 4. It may be an ammonium salt represented by ]. １ The number of carbon atoms may be 12 to 50, for example, 12 to 30.

[0094] Low molecular weight cationic dispersants may include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydropolyoxyethylene)ammonium chloride, benzyldodecyldi(hydropolyoxyethylene)ammonium chloride, N-[2-(diethylamino)ethyl]oleamide hydrochloride, etc.

[0095] The polymeric cationic dispersant may be various polymers (e.g., polyquaternium-1 to 47) having cationic groups (e.g., ammonium groups, quaternary ammonium groups). Examples of polymeric cationic dispersants include cationized starch, cationized cellulose (e.g., O-(2-hydroxy-3-(trimethylammonio)propylhydroxyethylcellulose chloride), cationized guar gum, cationized xanthan gum, chitosan, and other cationized natural products (especially cationized sugars); polymers of cationic group-containing monomers such as aziridine, vinylimidazole, aminoalkyl methacrylate, N,N,N',N'-tetramethyl-2-butene-1,4-diamine, quaternized dimethylammonium ethyl methacrylic acid, diallyldimethylammonium chloride, dimethylaminopropylamine, and quaternized vinylimidazole.

[0096] [Anionic Dispersant] The dispersant may contain an anionic dispersant. The anionic dispersant may be an anionic surfactant. The dispersant does not have to contain an anionic dispersant.

[0097] The anionic dispersant may be of low molecular weight or high molecular weight. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 100000 or less, 10000 or less, 7500 or less, 5000 or less, 25000 or less, 750 or less, or 250 or less.

[0098] Examples of anionic dispersants include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkanesulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfone fatty acid salts, N-acyl amino acid type dispersants, phosphate mono or diester type dispersants, and sulfosuccinate esters. An example of anionic dispersants is a carboxylate salt (e.g., a fatty acid salt).

[0099] [Amphoteric Dispersant] The dispersant may contain an amphoteric dispersant. The amphoteric dispersant may be an amphoteric surfactant.

[0100] The amphoteric dispersant may be of low molecular weight or high molecular weight. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 100000 or less, 10000 or less, 7500 or less, 5000 or less, 25000 or less, 750 or less, or 250 or less.

[0101] Examples of amphoteric dispersants include alanines, imidazolinium betaines, amide betaines, and betaine acetate. Specifically, these include lauryl betaine, stearyl betaine, laurylcarboxymethylhydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, and fatty acid amidopropyldimethylaminoacetic acid betaine.

[0102] [Inorganic Dispersant] The dispersant may contain an inorganic dispersant.

[0103] The average primary particle size of the inorganic dispersant may be 5 nm or larger, 30 nm or larger, 100 nm or larger, 1 μm or larger, 10 μm or larger, or 25 μm or larger, and may also be 100 μm or smaller, 50 μm or smaller, 10 μm or smaller, 1 μm or smaller, 500 nm or smaller, or 300 nm or smaller. The average primary particle size can be measured, for example, by observation with a microscope (scanning electron microscope or transmission electron microscope). The inorganic dispersant may also be hydrophilic particles.

[0104] Examples of inorganic dispersants include polyvalent metal phosphates such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, and hydroxyapatite; carbonates such as calcium carbonate and magnesium carbonate; silicates such as calcium metasilicate; sulfates such as calcium sulfate and barium sulfate; and hydroxides such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide.

[0105] [Amount of dispersant] The amount of dispersant may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, per 100 parts by weight of the liquid-repellent compound, or 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less.

[0106] [Liquid Medium] The repellent in this disclosure may include a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The repellent may be a dispersion or a solution. The repellent in this disclosure may include at least water, and in particular may be an aqueous dispersion.

[0107] 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 isopropyl alcohol), aromatic solvents (e.g., toluene and xylene), and petroleum solvents (e.g., alkanes with 5 to 10 carbon atoms, specifically naphtha and kerosene). The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent may contain compounds having at least one hydroxyl group (e.g., polyols such as alcohols and glycol-based solvents, ethers of polyols (e.g., monoethers)). These may be used individually or in combination of two or more.

[0108] [Amount of liquid medium] The amount of liquid medium may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, or 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, per 1 part by weight of the liquid-repellent compound. Alternatively, it may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less.

[0109] The amount of water may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, or 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, per 1 part by weight of the liquid-repellent compound.

[0110] The amount of organic solvent may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, per 1 part by weight of the liquid-repellent compound, or 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less.

[0111] [Wax] The repellent in this disclosure may include wax. Including wax can effectively impart liquid repellency to the substrate.

[0112] 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, with hydrocarbon waxes, particularly paraffin wax, being preferred. Specific examples of compounds that constitute the wax include n-alkanes (e.g., 1-alkenes, specifically tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatricontane, hexatriacontane) and n-alkenes (e.g., 1-eicosene, 1-docosene, 1-tricocene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, 1-nonacosene, 1-triaconcene, 1-hentriaconcene, 1-dotriacontane, tritriaconcene, 1-tetratriaconcene, 1-pentatriaconcene, 1-hexatriaconcene). The number of carbon atoms in the compounds that constitute the wax is preferably 20 to 60, for example, 25 to 45. The molecular weight of the wax may be 200 to 2000, for example, 250 to 1500 or 300 to 1000. These may be used alone or in combination of two or more.

[0113] The melting point of the wax may be 50°C or higher, 55°C or higher, 60°C or higher, 65°C or higher, or 70°C or higher, preferably 55°C or higher, and more preferably 60°C or higher. The melting point of the wax is measured in accordance with JIS K 2235-1991.

[0114] [Amount of wax] The amount of wax may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, per 100 parts by weight of the liquid-repellent compound. The amount of wax may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, per 100 parts by weight of the liquid-repellent compound.

[0115] [Silicone] The repellent in this disclosure may include silicone (polyorganosiloxane). The inclusion of silicone provides good liquid repellency.

[0116] As the silicone, known silicones can be used, and examples of silicones include polydimethylsiloxane and modified silicones (amino-modified, epoxy-modified, carboxy-modified, methylhydrogen silicone, etc.). The silicone may also be a silicone wax having waxy properties. These may be used alone or in combination of two or more.

[0117] The weight-average molecular weight of the silicone may be 1,000 or more, 10,000 or more, or 50,000 or more, and may also be 2,500,000 or less, 1,000,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, or 50,000 or less.

[0118] [Amount of Silicone] The amount of silicone may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, per 100 parts by weight of the liquid-repellent compound, or 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0119] [Yield-enhancing agent] The repellent agent in this disclosure may include a yield-enhancing agent. Yield-enhancing agents known in the papermaking field can be used, such as aluminum sulfate, acrylic polymers, starch, modified starch, cellulose, modified cellulose, silica, etc.

[0120] [Amount of yield agent] The amount of yield agent may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, or 500 parts by weight or more, per 100 parts by weight of the liquid-repellent compound, or 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0121] [Sizing Agent] The repellent agent in this disclosure may include a sizing agent. Sizing agents known in the papermaking field can be used, such as cationic sizing agents, anionic sizing agents, neutral sizing agents, and amphoteric sizing agents, and examples include rosin-based sizing agents (e.g., acidic rosin-based sizing agents, neutral rosin-based sizing agents)), alkyl ketene dimers, alkenyl succinic anhydride, etc.

[0122] [Amount of sizing agent] The amount of sizing agent may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, or 500 parts by weight or more, per 100 parts by weight of the liquid-repellent compound, or 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0123] [Organic Acids] The repellent of this disclosure may contain organic acids. Known organic acids can be used, for example, carboxylic acids, sulfonic acids, sulfinic acids, etc. are preferred, with carboxylic acids being particularly preferred. Examples of carboxylic acids 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 this disclosure, one organic acid may be used, or two or more may be used in combination.

[0124] [Amount of organic acid] The amount of organic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, per 100 parts by weight of the liquid-repellent compound, or 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0125] [Inorganic Acids] The repellent agent of this disclosure may contain an inorganic acid. Known inorganic acids can be used, and examples of inorganic acids include hydrogen chloride, hydrogen bromide, hydrogen iodide, nitric acid, boric acid, sulfuric acid, and phosphoric acid. In this disclosure, one inorganic acid may be used, or two or more may be used in combination.

[0126] [Amount of inorganic acid] The amount of inorganic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, per 100 parts by weight of the liquid-repellent compound, or 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0127] [pH adjuster] The repellent in this disclosure may include a pH adjuster. The pH adjuster may be an organic acid or inorganic acid or a salt thereof (for example, the organic acid or inorganic acid or a salt thereof as described above), or a base.

[0128] Specific examples of organic acids, inorganic acids, and their salts include lactic acid, carbon dioxide, succinic acid, gluconic acid, citric acid, trisodium citrate, phosphoric acid, potassium carbonate, and sodium bicarbonate.

[0129] Examples of bases include organic bases, inorganic bases, and salts thereof. Examples of organic bases include organic amines, basic amino acids (arginine, lysine, and their salts, etc.), guanidine and its salts (guanidine carbonate, etc.). Specifically, examples include alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, aminomethylpropanol (2-amino-2-methyl-1-propanol, etc.), aminomethylpropanediol (2-amino-2-methyl-1,3-propanediol, etc.), and alkylamines such as isopropylamine. These may be used individually or in combination of two or more.

[0130] Examples of inorganic bases include hydroxides, chlorides, silicates, carbonates, bicarbonates, metasilicates, phosphates, sulfates, and ammonia. Specifically, examples include alkali metal hydroxides such as sodium hydroxide, alkali metal carbonates such as sodium carbonate, alkali metal bicarbonates such as sodium bicarbonate, alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide, and alkaline earth metal carbonates such as magnesium carbonate and calcium carbonate. These may be used individually or in combination of two or more.

[0131] [Amount of pH adjuster] The amount of pH adjuster may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, or 500 parts by weight or more, per 100 parts by weight of the liquid-repellent compound, or 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less. The amount added may be adjusted so that the pH of the liquid-repellent agent is within a predetermined range.

[0132] [Fillers] The repellent agent in this disclosure may include fillers. Fillers known in the papermaking field can be used, such as talc, kaolin, calcium carbonate, titanium dioxide, and barium sulfate.

[0133] [Amount of Filler] The amount of filler may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, or 500 parts by weight or more, per 100 parts by weight of the liquid-repellent compound, or 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0134] [Paper Strength Enhancers] The paper repellent in this disclosure may include paper strength enhancers. Paper strength enhancers known in the papermaking field can be used, and examples include: polyacrylamide-based paper strength enhancers such as cationic polyacrylamide, anionic polyacrylamide, and amphoteric polyacrylamide; starch, enzyme-modified starch, thermochemically modified starch, oxidized starch, esterified starch, etherified starch (e.g., hydroxyethylated starch), aldehyde starch, cationic starch, starch, xanthan gum, karaya gum, welan gum, guar gum, pectin, tamarind gum, carrageenan, chitosan, gum arabic, locust bean gum, cellulose, alginic acid, agar, dextran, cellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, chitin nanofibers, cellulose nanofibers, cellulose nanocrystals, and pullulan, and polysaccharides thereof (e.g., modified polysaccharides into which hydroxyl groups or cationic groups have been introduced) and other polysaccharide-based paper strength enhancers; Examples of paper strength enhancers include polyamide resins, polyamine resins, polyamide-polyamine resins, polyamide-epichlorohydrin resins, polyamide-polyamine-epichlorohydrin resins, polyamide-polyurea-formaldehyde resins, and epoxidized polyamide resins; urea / melamine-based paper strength enhancers such as urea resins, melamine resins, urea-formaldehyde resins, and melamine-formaldehyde resins; polyvinyl alcohol-based paper strength enhancers such as polyvinyl alcohol, fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, ethylene-modified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol, cation-modified polyvinyl alcohol, diacetone-modified polyvinyl alcohol, and terminal alkyl-modified polyvinyl alcohol; and styrene-butadiene copolymers, polyvinyl acetate, vinyl chloride-vinyl acetate copolymers, polyvinyl chloride, polyvinylidene chloride, polyacrylic acid esters, fatty acid diamides, polyethyleneimine resins, and ketone aldehyde resins.

[0135] [Amount of paper strength enhancer] The amount of paper strength enhancer may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, or 500 parts by weight or more, per 100 parts by weight of the liquid-repellent compound, or 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0136] [Other Components] The repellent agent may contain other components besides those listed above. Examples of other components include flocculants, coagulants, binder resins, preservatives, antibacterial agents, deodorants, fragrances, etc. These may be used alone or in combination of two or more. In addition to the above components, other components may include other water and / or oil repellents, dispersants, softeners, flame retardants, paint fixatives, drying speed regulators, crosslinking agents, film-forming aids, compatibilizers, viscosity modifiers, pH adjusters, insecticides, defoamers, shape retainers, pigments, clays, polymer dispersants, stain removers, enzymes such as cellulase, amylase, protease, lipase, and keratinase as fiber surface modifiers, and antifoaming agents. These may be used alone or in combination of two or more. The repellent agent may also contain the components of the pulp composition listed below.

[0137] [Amount of other components] The amount of each or total amount of other components may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, or 500 parts by weight or more, per 100 parts by weight of the liquid-repellent compound, or 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0138] <Pulp Composition> The pulp composition in this disclosure comprises a liquid-repellent compound and a pulp base material. The pulp composition in this disclosure may exhibit excellent oil resistance and / or water resistance, preferably both.

[0139] The pulp composition in this disclosure is obtained by adding a liquid-repellent compound to a pulp base material. The pulp composition may also be obtained by treating the pulp base material with a repellent containing a liquid-repellent compound, where the amount and composition of the repellent may be adjusted so that each component is in a desired amount. Each component that may be included in the repellent may be added to the pulp composition separately as an additive.

[0140] The pulp composition in this disclosure does not necessarily have to contain any of the compounds selected from the group consisting of compounds having 8 or more carbon atoms in a fluoroalkyl group, compounds having 8 or more carbon atoms in a perfluoroalkyl group, compounds having 4 or more carbon atoms in a fluoroalkyl group, compounds having 4 or more carbon atoms in a perfluoroalkyl group, compounds having a perfluoroalkyl group, compounds having a fluoroalkyl group, and compounds having a fluorine atom. The pulp composition in this disclosure can impart liquid repellency to a substrate even without containing these fluorine compounds.

[0141] The pH of the pulp composition may be 3 to 10, for example 5 to 9, and particularly 6 to 8, and the amounts of each component may be adjusted to achieve such a pH.

[0142] [Pulp-based material] The pulp composition includes a pulp-based material. The pulp-based material is composed of pulp, which may be wood pulp, non-wood pulp, recycled paper pulp, etc., and may also include bagasse pulp, for example.

[0143] [Wood Pulp] Wood pulp includes coniferous kraft pulp obtained from genera such as fir and pine, and hardwood kraft pulp obtained from genera such as acacia, eucalyptus, beech, and aspen (for example, poplar). Examples of coniferous kraft pulp include unbleached coniferous kraft pulp (NUKP), bleached coniferous kraft pulp (NBKP), semi-bleached coniferous kraft pulp (NSBKP), and sulfite coniferous pulp. Examples of hardwood kraft pulp include unbleached hardwood kraft pulp (LUKP), bleached hardwood kraft pulp (LBKP), semi-bleached hardwood kraft pulp (LSBKP), and sulfite hardwood pulp. The pulp used may be used alone or in combination. In addition to kraft pulp, there are also softwood kraft pulp and hardwood kraft pulp, as well as mechanical pulps such as stone ground pulp (SGP), pressure stone ground pulp (PGW), refiner ground pulp (RGP), thermo ground pulp (TGP), chemiground pulp (CGP), crushed wood pulp (GP), and thermomechanical pulp (TMP). Furthermore, recycled paper pulp includes disintegrated recycled paper pulp, disintegrated and deinked recycled paper pulp, or disintegrated, deinked and bleached recycled paper pulp, which are produced from brown recycled paper, recycled kraft envelopes, recycled magazines, recycled newspapers, recycled flyers, recycled office paper, recycled cardboard, recycled white recycled paper, recycled Kent paper, recycled imitation paper, recycled land deed paper, etc.

[0144] [Non-wood pulp] Examples of non-wood pulp include pulp obtained from bagasse, kenaf, bamboo, linter, cotton, linen, hemp, ramie, straw, esparto, Manila hemp, sisal hemp, jute, flax, ganpi, mitsumata, kozo, etc.

[0145] [Pulp Fiber Morphology] From the viewpoint of improving oil resistance, the average fiber length of the pulp is preferably 0.1 mm or more, more preferably 0.3 mm or more, and even more preferably 0.5 mm or more. 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.

[0146] From the viewpoint of improving oil resistance, the average fiber diameter of the pulp is preferably 5 μm or more, more preferably 10 μm or more, even more preferably 15 μm or more, and also preferably 50 μm or less, more preferably 40 μm or less, and even more preferably 30 μm or less.

[0147] [Composition of pulp base material] When bagasse pulp is used, the amount may be more than 0% by weight, 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 in the pulp base material, preferably 20% or more by weight, and may also be 100% or less by weight, 90% or less by weight, 80% or less by weight, 70% or less by weight, 60% or less by weight, 50% or less by weight, 40% or less by weight, 30% or less by weight, 20% or less by weight, or 10% or less by weight, for example, 80% or less by weight.

[0148] The total amount of pulp other than bagasse may be 0% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more in the pulp base material, and may also be 99% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, or 10% by weight or less.

[0149] The amount of wood pulp may be 0% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more in the pulp base material, and may also be 99% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, or 10% by weight or less.

[0150] [Form of pulp substrate] The form of the pulp substrate when a liquid-repellent compound is added may be pulp alone, pulp slurry, pulp products, etc. Specific examples include bleached or unbleached chemical pulps such as kraft pulp and sulfite pulp, bleached or unbleached high-yield pulps such as wood pulp, mechanical pulp or thermomechanical pulp; pulp slurry containing the pulp; and pulp products such as paper, paper containers, and pulp molded articles.

[0151] [Amount of pulp base material] The amount of pulp base material may be 0.1% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 50% by weight or more, 75% by weight or more, or 90% by weight or more in the pulp composition, and may also be 99% by weight or less, 75% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, 4% by weight or less, or 3% by weight or less. Typically, when the pulp composition is prepared by internal additives, the amount of pulp base material is 30% by weight or less in the pulp composition, and when the pulp composition is prepared by external additives, the amount of pulp base material may be 75% by weight or more in the pulp composition.

[0152] The amount of pulp base material may be 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, 90% by weight or more, 95% by weight or more, or 99% by weight or more in the pulp composition excluding the liquid medium, and may also be 99.9% by weight or less, 95% by weight or less, 90% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, or 55% by weight or less.

[0153] [Liquid Media] The pulp composition may contain a liquid media. The liquid media may be water, an organic solvent, or a mixture of water and an organic solvent, and is typically an aqueous media, especially water. The liquid media may also contain a liquid media derived from a repellent.

[0154] [Amount of liquid medium] The amount of liquid medium may be 0.1% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 50% by weight or more, 75% by weight or more, 90% by weight or more, or 95% by weight or more in the pulp composition, and may also be 99% by weight or less, 75% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, 4% by weight or less, or 3% by weight or less. Typically, when the pulp composition is prepared by internal additives, the amount of liquid medium is 50% by weight or more, particularly 90% by weight or more in the pulp composition, and when the pulp composition is prepared by external additives, the amount of liquid medium is 30% by weight or less, particularly 10% by weight or less in the pulp composition.

[0155] [Liquid-repellent compounds] The pulp composition contains liquid-repellent compounds. For details on liquid-repellent compounds, refer to the explanation of liquid-repellent compounds in <Repellents (oil and water resistant agents)>.

[0156] [Amount of liquid-repellent compound] The amount of liquid-repellent compound may be 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more relative to the pulp substrate, preferably 0.5% by weight or more, and may also be 25% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, for example, 15% by weight or less, 5.0% by weight or less, or 3.0% by weight or less.

[0157] The liquid-repellent compound may be applied as an external additive to the surface of a pulp substrate (e.g., pulp products such as paper, paper containers, and pulp molded articles), and the amount of the liquid-repellent compound contained in the coating layer formed by the external additive treatment is 0.01 g / m². 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 1.0 g / m ２The above is sufficient, and also 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 The following, or 0.1 g / m ２ The following is acceptable:

[0158] [Dispersant] The pulp composition may contain a dispersant. For details on the types of dispersants, refer to the explanation of dispersants in <Repellents (Oil and Water Resistant Agents)>.

[0159] [Amount of dispersant] The amount of dispersant may be 0.001% by weight or more, 0.01% by weight or more, 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 relative to the pulp substrate, and may also be 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, preferably 5.0% by weight or less, more preferably 3.0% by weight or less.

[0160] [Paper Strength Enhancers] The pulp composition may contain paper strength enhancers. For details on the types of paper strength enhancers, refer to the explanation of paper strength enhancers in <Repellents (Oil and Water Resistants)>.

[0161] [Amount of paper strength enhancer] The amount of paper strength enhancer may be 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more relative to the pulp, and may also be 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, preferably 5.0% by weight or less.

[0162] [Sizing Agents] Pulp compositions may contain sizing agents. For details on the types of sizing agents, refer to the explanation of sizing agents in <Repellents (Oil and Water Resistants)>.

[0163] [Amount of sizing agent] The amount of sizing agent may be 0.1% by weight or more, 0.2% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more relative to the pulp, and may also be 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less.

[0164] [Binder] The pulp composition may contain a binder. The binder is used to improve the binding between pulp fibers. Examples of binders include non-water-soluble binders such as polyester resins, polyurethane resins, styrene-butadiene resins, vinyl acetate resins, ethylene-vinyl acetate resins, acrylonitrile-butadiene resins, polyethylene resins, polypropylene resins, carboxymethylcellulose resins, polyamide resins, vinyl chloride resins, and vinylidene chloride resins, as well as water-soluble binders such as casein.

[0165] [Amount of Binder] The amount of binder may be 0.1% by weight or more, 0.2% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more relative to the pulp, and may also be 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less.

[0166] [Pigments] The pulp composition may contain pigments. Examples of pigments include inorganic pigments such as kaolin, light calcium carbonate, heavy calcium carbonate, magnesium carbonate, magnesium oxide, aluminum hydroxide, alumina, silica, magnesium aluminosilicate, calcium silicate, white carbon, bentonite, zeolite, sericite, smectite, calcium sulfate, barium sulfate, synthetic mica, titanium dioxide, and zinc oxide; as well as polydienes such as polyisoprene, polyneoprene, and polybutadiene; polyalkenes such as polybutene, polyisobutylene, and polypropylene; polymers and copolymers of vinyl monomers such as vinyl acetate, styrene, (meth)acrylic acid, alkyl (meth)acrylate, (meth)acrylamide, and methyl vinyl ether; and organic pigments such as various dense, hollow, or through-porous particles of polyurethane resins, polyester resins, polyamide resins, urea resins, melamine resins, and benzoguanamine resins.

[0167] [Amount of pigment] The amount of pigment may be 0.1% by weight or more, 0.2% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more relative to the pulp, and may also be 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less.

[0168] [Synthetic Fibers] The pulp composition may contain synthetic fibers. Examples of synthetic fibers include polyester, polyamide, polyolefin, acrylic, nylon, vinylon, ceramics, rayon, acetate, etc.

[0169] [Amount of synthetic fibers] The amount of synthetic fibers may be 0.1% by weight or more, 0.5% by weight or more, 1.0% by weight or more, 2.0% by weight or more, 3.0% by weight or more, 5.0% by weight or more, or 10% by weight or more relative to the pulp, and may also be 50% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 3.0% by weight or less, or 1.0% by weight or less.

[0170] [Other Additives] In addition to the above, the pulp composition may also contain other additives such as fixing agents (aluminum sulfate, etc.), coagulants / flocculants (polyamine resins, etc.), yield improvers (polyacrylamide resins, etc.), organic acids (formic acid, acetic acid, etc.), dyes, slime control agents, defoamers, polycarboxylic acids, waxes, and penetrants, which are paper-use chemicals used in the manufacture of pulp products.

[0171] [Amount of other additives] The amount of other additives may be 0.01% by weight or more, 0.1% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, based on the pulp base material, or 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, 3% by weight or less, or 1% by weight or less.

[0172] <Method for producing pulp composition / pulp product> The pulp composition in this disclosure can be obtained by treating a pulp substrate with a liquid-repellent agent containing a liquid-repellent compound.

[0173] The obtained pulp composition can be subjected to processing steps such as drying, heating, and molding as needed to obtain pulp products.

[0174] The repellent agent in this disclosure can be applied to a pulp substrate by conventionally known methods as a treatment agent (particularly a surface treatment agent). The treatment method may involve diluting the repellent agent in this disclosure by dispersing it in an organic solvent or water as needed, and then applying it to the interior and / or surface of the pulp substrate by known methods such as immersion coating, spray coating, or foam coating, followed by drying. The dilution ratio may be appropriately changed depending on the concentration and application of the repellent agent, but may be 3 to 2000 times, for example, 10 to 100 times. After drying, a pulp product with the solid components of the repellent agent attached is obtained. If necessary, curing may be performed by applying an appropriate agent together with the repellent agent.

[0175] The repellent can be applied to the pulp substrate by any known method for treating the pulp substrate with a liquid. The pulp substrate may be immersed in the repellent, the pulp substrate and the repellent may be mixed, or the solution may be applied to or sprayed onto the pulp substrate. The treated pulp substrate is preferably dried and cured by heating to develop liquid repellency. The heating temperature may be, for example, 100°C to 200°C, 100°C to 170°C, or 100°C to 120°C. In this disclosure, the heating time may be 5 seconds to 60 minutes, for example, 30 seconds to 3 minutes.

[0176] As a method for processing pulp substrates, an internal processing method in which a repellent is added to the pulp substrate before papermaking (e.g., in the form of a pulp slurry) or an external processing method in which a repellent is applied to the pulp substrate after papermaking (e.g., a pulp product) can be used. Examples of internal processing methods include mixing and immersion, and may include a step of adding a repellent to the pulp slurry and stirring and mixing it. Examples of external processing methods include spraying, coating, immersion, and foam coating, and specifically include a pound-type two-roll size press, a gate-roll type, and a rod-metering size press. The processing may be either external or internal. For example, when the pulp substrate is paper, the paper may be coated, or the solution may be attached to or sprayed onto the paper, or it may be mixed with the pulp slurry before papermaking. When the pulp substrate is a fibrous material, examples of processing methods include padding, immersion, spraying, and coating. For padding treatment, for example, methods using padding equipment described on pages 396-397 of the Dictionary of Textile Dyeing and Processing (published in 1963 by Nikkan Kogyo Shimbun) and pages 256-260 of Color Dyeing Chemistry III (published in 1975 by Jikkyo Shuppan Co., Ltd.) can be used. For coating treatment, for example, methods using coating machines described on pages 473-477 of the General Catalog of Dyeing and Finishing Equipment (published in 1981 by Senryo-sha) can be used. For immersion treatment, for example, methods using batch-type dyeing machines described on pages 196-247 of the General Catalog of Dyeing and Finishing Equipment (published in 1981 by Senryo-sha) can be used, and liquid flow dyeing machines, air flow dyeing machines, drum dyeing machines, winch dyeing machines, washer dyeing machines, cheese dyeing machines, etc. can be used. For spray treatment, for example, methods using air sprays that atomize the treatment liquid with compressed air and spray it, or air sprays using a liquid pressure atomization method can be used.

[0177] The processing method may be an internal additive treatment in which a repellent is added to the pulp slurry before papermaking. The internal additive treatment may include, but is not limited to, one or more of the following steps: adding a repellent to the pulp slurry and stirring and mixing it; dewatering the pulp composition prepared in the first step by suction through a mesh of a predetermined shape to deposit the pulp composition and form a pulp molded intermediate; and molding and drying the pulp molded intermediate using a heated mold to obtain a pulp molded product. After simple drying at room temperature or high temperature, the processed paper may optionally be heat-treated depending on the properties of the paper. The heat treatment temperature may be 150°C or higher, 180°C or higher, or 210°C or higher, and may be 300°C or lower, 250°C or lower, or 200°C or lower, and may be particularly 80°C to 180°C. By performing heat treatment in such a temperature range, excellent oil resistance and water resistance can be obtained. The pulp substrate, which has undergone internal additive treatment, may be further treated externally with a repellent agent to deposit additional liquid-repellent compounds on its surface.

[0178] The processing method may be an external additive treatment in which a repellent is applied to the pulp substrate after papermaking. The sizing press for external additive treatment can also be classified as follows according to the application method. One application method is the so-called pound-type two-roll sizing press, in which a coating liquid (sizing liquid) is supplied to the nip portion formed by passing the paper between two rubber rolls, creating a coating liquid reservoir called a pound, and the sizing liquid is applied to both sides of the paper by passing the paper through this reservoir. Other application methods are the gate-roll type and the rod-metering sizing press, in which the sizing liquid is applied by a surface transfer type. In the pound-type two-roll sizing press, the sizing liquid easily penetrates into the interior of the paper, while in the surface transfer type, the sizing liquid components tend to remain on the surface of the paper. Compared to the pound-type two-roll sizing press, the surface transfer type allows the coating layer to remain on the surface of the paper more easily, and the coating layer formed on the surface is greater than that of the pound-type two-roll sizing press. In this disclosure, performance can be imparted to the paper even when the former pound-type two-roll sizing press is used. Paper processed in this manner can exhibit excellent oil and water resistance after simple drying at room temperature or high temperature, and optionally, depending on the properties of the paper, undergo heat treatment up to 300°C, for example, up to 200°C, and particularly within a temperature range of 80°C to 180°C.

[0179] The pulp product is preferably a pulp molded product. The pulp molded product can be manufactured by a method that includes preparing a blended pulp slurry by adding a repellent to a slurry in which pulp is dispersed in an aqueous medium, forming a pulp molded intermediate, dewatering it, and then drying it to obtain a pulp molded product.

[0180] The proportion of each component in the blended pulp slurry relative to the pulp (slurry) (overall standard) can be appropriately selected according to the desired physical properties of the pulp molded product and to achieve a high degree of filtration suitable for papermaking and dewatering, but may be as follows, for example: • Aqueous medium 89.5 to 99.89% by weight, e.g., 94.5 to 99.69% by weight • Pulp 0.1 to 5% by weight, e.g., 0.3 to 2.5% by weight • Repelling agent (solids) 0.001 to 2.79% by weight, especially 0.005 to 1.05% by weight • Liquid-repellent compound 0.00001 to 1% by weight, e.g., 0.0001 to 0.5% by weight

[0181] The electrical conductivity of the blended pulp slurry should be between 0.1 and 2000 μS / cm, 0.1 and 1000 μS / cm, 1 and 800 μS / cm, or 10 and 500 μS / cm. Within this range, high oil resistance can be obtained. The pH of the blended pulp slurry should be between 4 and 9, 5 and 8 is better, and 6 and 7 is even better. Within this range, high oil resistance can be obtained. The hardness of the water used in the blended pulp slurry should be 5000 ppm or less, 3000 ppm or less is better, 1000 ppm or less is particularly good, and 500 ppm or less is exceptionally good. Within this range, high oil resistance can be obtained.

[0182] Next, a pulp mold intermediate is formed from the prepared pulp slurry, dehydrated, and then at least dried to obtain a pulp mold product.

[0183] Papermaking, dehydration, and drying can be carried out according to conventionally known methods for pulp molds.

[0184] For example, by filtering and dewatering the prepared pulp slurry using a mold of a desired shape with numerous pores (a filter may be provided if necessary), (e.g., by suction and / or reduced pressure), the aqueous medium can be at least partially removed from the prepared pulp slurry, and a pulp mold intermediate having a shape corresponding to the mold can be obtained.

[0185] Drying may be carried out at a temperature that can effectively remove any remaining aqueous medium, for example, 90–250°C, particularly 100–200°C. The drying time is not particularly limited and can be selected so that the aqueous medium remaining in the pulp mold intermediate is substantially removed. The drying atmosphere is not particularly limited and can be simply the ambient atmosphere (air at normal pressure).

[0186] During and / or thereafter, if necessary, other conventionally known processes in the pulp mold, such as press molding (including heat pressing), may be carried out.

[0187] As described above, pulp molded products can be manufactured. Such pulp molded products contain pulp and a repellent, and can achieve high gas barrier properties and excellent water and oil resistance.

[0188] The proportion of pulp, repellents, etc., in pulp molded products can be considered substantially equal to the proportion of solids in the raw materials used (although aqueous media and other liquid media, if present, can usually be removed by drying and press molding, solids may remain without being removed or decomposed).

[0189] In pulp molded products, the content ratio of each component (components that may remain in the pulp molded product) relative to the pulp (solid content) can be appropriately selected according to the desired physical properties of the pulp molded product, but for example, it may be as follows: • Liquid-repellent compound: 0.01 to 10% by weight, 0.01 to 5% by weight, or 0.05 to 2% by weight

[0190] Pulp molded products can be manufactured by adding a repellent (by adding it to a pulp slurry and manufacturing it using the pulp molding method). Therefore, after use, the entire pulp molded product can be crushed and returned to its original raw material, making it suitable for recycling. Furthermore, since such pulp molded products can utilize the inherent biodegradability of pulp, the environmental burden can be made extremely small, preferably virtually eliminated. In addition, such pulp molded products can retain the texture of pulp on the surface of the product, and do not develop a glossy appearance that would be impaired if the surface were laminated with a plastic film.

[0191] Such pulp molded products can be suitably used as food containers (including trays, etc.), for example, as storage containers for frozen foods and chilled foods.

[0192] Specific examples of pulp products include paper, paper containers, pulp molded articles, food packaging materials, food containers, gypsum board base paper, coated base paper, medium-grade paper, general liners and cores, neutral pure white roll paper, neutral liners, rust-preventive liners and metal interleaving paper, kraft paper, neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper, and neutral information paper. Suitable examples of pulp products include food packaging materials and food containers, and in particular, pulp molded articles for food contact applications.

[0193] Although embodiments have been described above, it should be understood that various modifications to the form and details are possible without departing from the spirit and scope of the claims.

[0194] Next, the present disclosure will be specifically described with reference to examples and comparative examples. However, these descriptions will not limit the present disclosure. In the following, parts, percentages, or ratios refer to parts by weight, weight percentages, and weight ratios, respectively, unless otherwise specified. The test method is as follows.

[0195] <Preparation of processed paper> A pulp slurry was prepared using wood pulp with a weight ratio of LBKP (bleached hardwood kraft pulp) and NBKP (bleached softwood kraft pulp) of 60% by weight and 40% by weight, and a pulp filtration degree of 400 ml (Canadian Standard Freeness). A wet strength agent and a sizing agent were added to this pulp slurry and paper was produced using a wire screen paper machine with a paper density of 0.60 g / cm³. ３ Basis weight 42 g / m² ２ This paper was used as the base paper for external processing (size press processing). The oil resistance (KIT value) of this base paper was 0, and the water resistance (Cobb value) was 52 g / m². ２ That was the case.

[0196] <Preparation of Oil-Resistant Paper> Aqueous dispersions of eight compounds A to H shown in Table 1 and starch were prepared. The treated solutions were then processed in a size press and dried in a drum dryer to obtain oil-resistant paper. The obtained oil-resistant paper was used as test paper, and KIT tests, practical oil resistance evaluation, and water resistance evaluation were performed. Hydroxyethylated starch was used as the starch. Octenyl succinate starch was used as the hydrophobic starch. For the size press treatment (using a Mathis size press), a so-called pound-type two-roll size press treatment was used, in which the treatment solution was stored between the rolls and the base paper was passed through the treatment solution between the rolls at an arbitrary roll speed and nip pressure.

[0197] [Table 1] Compounds A to H

[0198] <KIT Test (Oil Resistance)> Measurement was performed using the 3M Kit Test (TAPPI T-559cm-02). The 3M Kit Test method involved placing a test oil containing castor oil, toluene, and heptane onto the surface of treated paper, and evaluating the oil resistance by wiping off the test oil after 15 seconds, and checking for the presence or absence of oil stains on the treated paper. Tests were conducted with test oils from kit numbers 1 to 6, and the kit number with the highest number of no stains observed was used as the evaluation result for oil resistance.

[0199] <Evaluation of Practical Oil Resistance (Oil Resistance)> Canola oil was placed on the surface of the treated paper, and the degree of oil penetration was checked after 15 seconds. The evaluation values ​​were set as follows according to the degree of penetration: 5: 0-5% 4: 6-20% 3: 21-50% 2: 51-75% 1: 76-100%

[0200] <Water Resistance Evaluation> Pure water was placed on the surface of the treated paper, and the degree of water penetration was checked after 60 seconds. The evaluation values ​​were set as follows according to the degree of penetration: 3: 0-20% 2: 21-50% 1: 51-100%

[0201] <Example 1> A treatment solution was prepared by adjusting the solid content of an aqueous dispersion of compound A to 4.8% by weight. The treatment solution was then applied externally, followed by a KIT test of the treated paper, evaluation of its oil resistance to practical oils, and evaluation of its water resistance. The results are shown in Table 2.

[0202] <Example 2> The same procedure as in Example 1 was used for processing and evaluation, except that compound A was replaced with compound B. The results are shown in Table 2.

[0203] <Example 3> The same procedure as in Example 1 was used for processing and evaluation, except that compound A was replaced with compound C. The results are shown in Table 2.

[0204] <Example 4> A treatment solution was prepared by adding a solution to an aqueous dispersion of compound A so that the solid content was 2.4% by weight and the starch solid content concentration was 7% by weight. The treatment solution was then added externally, and the treated paper underwent a KIT test, practical oil resistance evaluation, and water resistance evaluation. The results are shown in Table 2.

[0205] <Example 5> The same procedure as in Example 4 was used for processing and evaluation, except that compound A was replaced with compound B. The results are shown in Table 2.

[0206] <Example 6> The same procedure as in Example 4 was used for processing and evaluation, except that compound A was replaced with compound C. The results are shown in Table 2.

[0207] <Example 7> The same procedure as in Example 4 was used for processing and evaluation, except that compound A was replaced with compound D. The results are shown in Table 2.

[0208] <Example 8> The same method as in Example 4 was used for processing and evaluation, except that the starch was changed to hydrophobized starch. The results are shown in Table 2.

[0209] <Example 9> A treatment solution was prepared using a dispersion of compound A with a solid content of 2.4% by weight, an acrylic emulsion (Boncoat R-3380-E, manufactured by DIC) with a solid content of 1.2% by weight, and a starch solid content concentration of 5.8% by weight. The treatment solution was then applied externally, followed by a KIT test of the treated paper, evaluation of its oil resistance to practical oils, and evaluation of its water resistance. The results are shown in Table 2.

[0210] <Example 10> 150 parts of a dispersion of compound A (solid content 7% by weight) and 50 parts of ion exchange resin were stirred for 10 minutes. The mixture was then filtered, the filtrate was dried, and compound J was recovered by ion exchange of the sodium salt of compound A with acid. The same procedure as in Example 1 was used for processing and evaluation, except that compound A was replaced with compound J. The results are shown in Table 2.

[0211] <Example 11> 150 parts of a dispersion of compound B (solid content 7% by weight) and 50 parts of ion exchange resin were stirred for 10 minutes. The mixture was then filtered, the filtrate was dried, and compound K was recovered by ion exchange of the potassium salt of compound B with acid. The same procedure as in Example 1 was used for processing and evaluation, except that compound A was replaced with compound K. The results are shown in Table 2.

[0212] <Comparative Example 1> A treatment solution was prepared so that the solid content concentration of hydrophobic starch was 7% by weight. The treatment solution was then applied externally, and a KIT test and practical oil resistance evaluation were performed on the treated paper. The results are shown in Table 2.

[0213] <Comparative Example 2> A treatment solution was prepared by adding a solid content of 2.4% by weight to an aqueous dispersion of compound E and a starch solid content concentration of 7% by weight. The treatment solution was then subjected to external additive treatment, a KIT test was performed on the treated paper, and the oil resistance of practical oils was evaluated. The results are shown in Table 2.

[0214] <Comparative Example 3> A treatment solution was prepared by adjusting the aqueous dispersion of compound F to have a solid content of 2.4% by weight and a starch solid content concentration of 7% by weight. The treatment solution was then subjected to external additive treatment, a KIT test was performed on the treated paper, and the oil resistance of practical oils was evaluated. The results are shown in Table 2.

[0215] <Comparative Example 4> A treatment solution was prepared by adding a solid content of 2.4% by weight to an aqueous dispersion of compound G and a starch solid content concentration of 7% by weight. The treatment solution was then subjected to external additive treatment, a KIT test was performed on the treated paper, and the oil resistance of practical oils was evaluated. The results are shown in Table 2.

[0216] <Comparative Example 5> A treatment solution was prepared by adjusting the aqueous dispersion of compound H to have a solid content of 2.4% by weight and a starch solid content concentration of 7% by weight. The treatment solution was then subjected to external additive treatment, a KIT test was performed on the treated paper, and the oil resistance of practical oils was evaluated. The results are shown in Table 2.

[0217] [Table 2]

[0218] The oil and water resistant agents of this disclosure are applicable to various types of paper, particularly paper used in food containers and food packaging materials. The oil and water resistant agents are incorporated into the paper by external or internal addition, particularly internal addition.

Claims

1. An oil and water resistant agent for pulp comprising a liquid-repellent compound which is a modified organic acid or a salt thereof, wherein the liquid-repellent compound has a monovalent hydrocarbon group having 4 to 50 carbon atoms, a polar bond, and an acidic group or a salt thereof.

2. The oil- and water-resistant agent according to claim 1, wherein the liquid-repellent compound is a salt of the modified organic acid.

3. The oil and water resistant agent according to claim 1 or 2, wherein the monovalent hydrocarbon group is an alkyl group having 11 or more carbon atoms.

4. The oil and water resistant agent according to any one of claims 1 to 3, wherein the liquid-repellent compound has a structure comprising an aliphatic hydrocarbon group, the polar bond, and the acidic group or a salt thereof, and the molecular weight of the liquid-repellent compound is 2000 or less.

5. The oil and water resistant agent according to any one of claims 1 to 4, wherein the polar bond is selected from the group consisting of amide bonds, urethane bonds, urea bonds, and imide bonds.

6. The acidic group or its salt is -COOM, -SO ３ M, -OSO ３ M, and -PO ４ M, -P (=O) (OM) ２ An oil and water resistant agent according to any one of claims 1 to 5, selected from the group consisting of [wherein M is independently a hydrogen atom or a cation].

7. The liquid-repellent compound is represented by the following formula: R １ -A-R ２ (B １ )(R ３ -B ２ ) ｎ [In the formula, R １ is a monovalent aliphatic hydrocarbon group having 4 to 50 carbon atoms, A is a polar bond, R ２ is -CH ２ - or -CH(-) ２ , B １ is an acidic group or a salt thereof, R ３ is a direct bond or a divalent aliphatic hydrocarbon group having 1 to 40 carbon atoms, B ２ is an acidic group or a salt thereof, and n is 0 or 1.] The oil- and water-resistant agent according to any one of claims 1 to 6.

8. R １ A is an alkyl group having 11 or more carbon atoms, A is selected from the group consisting of amide bonds, urethane bonds, urea bonds, and imide bonds, and B １ and B ２ However, they are independent of each other: -COOM, -SO ３ M, -OSO ３ M, -PO ４ M, and -P (=O) (OM) ２ Selected from the group consisting of [wherein M is independently a hydrogen atom or a cation], B １ and B ２ The oil and water resistant agent according to claim 7, wherein at least one of the members comprises a carboxylic acid group or a salt thereof.

9. An oil- and water-resistant agent according to any one of claims 1 to 8, comprising a water-soluble polymer.

10. An oil- and water-resistant agent according to any one of claims 1 to 9, which is a water-dispersible composition.

11. An oil- and water-resistant agent according to any one of claims 1 to 10, comprising a dispersant.

12. An oil- and water-resistant agent according to any one of claims 1 to 11, comprising at least one selected from the group consisting of yield agents, sizing agents, pH adjusters, fillers, and paper strength enhancers.

13. A pulp product to which solid components of the oil- and water-resistant agent described in any one of claims 1 to 12 are attached.

14. The pulp product according to claim 13, which is a food packaging material or a food container.

15. A method for producing pulp products, comprising treating a pulp substrate with an oil- and water-resistant agent according to any one of claims 1 to 12.

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