Agent for imparting oil resistance

Abstract

The present invention provides an agent for imparting oil resistance which includes a wax, wherein the wax gives a 1H-NMR spectrum in which the ratio of the integral [integral B] of a signal observed in the chemical shift range of 1.05-1.47 ppm to the integral [integral A] of a signal observed in the chemical shift range of 0.79-0.93 ppm, [integral B] / [integral A], is 9 or greater.

Description

Oil resistant agent

[0001] The present disclosure relates to repellents, particularly oil repellents.

[0002] Patent Document 1 discloses a paper substrate for an oxygen-absorbing packaging material containing a wax having a melting point of 50°C or more and 80°C or less.

[0003] Japanese Patent Application Laid-Open No. 2023-113289

[0004] Patent Document 1: １ There is no description or suggestion of an oil-resistant agent containing a wax having a specific chemical shift value in a H-NMR spectrum and / or a specific peak intensity in a variable-temperature X-ray diffraction measurement.

[0005] An object of the present disclosure is to provide a novel oil-proofing agent that can impart oil resistance to a substrate (particularly a pulp substrate).

[0006] The present disclosure includes the following aspects: [Item 1] An oil-resistant agent containing a wax, １An oil-resistant agent, wherein the integral ratio [integral B] / [integral A] between the integral [integral A] of a signal observed in a chemical shift range of 0.79 ppm to 0.93 ppm in a H-NMR spectrum and the integral [integral B] of a signal observed in a chemical shift range of 1.05 ppm to 1.47 ppm in a H-NMR spectrum is 9 or greater. [Item 2] The oil-resistant agent according to Item 1, wherein, in a variable-temperature X-ray diffraction measurement of the wax, the diffraction intensity ratio [A60°C] / [A25°C] between the maximum peak intensity [A25°C] at a measurement temperature of 25°C and the maximum peak intensity [A60°C] at a measurement temperature of 60°C in a 2θ range of 15° to 30° is 0.3 or greater. [Item 3] The oil-resistant agent according to Item 1 or 2, wherein the wax is a petroleum wax. [Item 4] The oil-resistant agent according to any one of Items 1 to 3, wherein the wax is at least one wax selected from the group consisting of paraffin wax and microcrystalline wax. [Item 5] The oil-resistant agent according to any one of Items 1 to 4, wherein the melting point of the wax is 55°C or higher. [Item 6] The oil-resistant agent according to any one of Items 1 to 5, wherein the oil-resistant agent is an aqueous dispersion. [Item 7] The oil-resistant agent according to any one of Items 1 to 6, wherein the oil-resistant agent contains a dispersant, and the dispersant is at least one selected from the group consisting of nonionic dispersants, anionic dispersants, and cationic dispersants. [Item 8] The oil-resistant agent according to any one of Items 1 to 7, wherein the oil-resistant agent is an aqueous dispersion, wherein the oil-resistant agent contains a dispersant, and wherein the volume median diameter (D50) of the oil-resistant agent measured by a laser diffraction scattering method is 0.01 μm or more and 1 μm or less. [Item 9] The oil-resistant agent according to any one of Items 1 to 8, wherein the charge density is -600 μeq / g or more and 600 μeq / g or less. [Item 10] The oil-resistant agent according to any one of Items 1 to 9, wherein the oil-resistant agent contains a liquid medium, and wherein, in a variable-temperature X-ray diffraction measurement of a residue obtained by removing the liquid medium from the oil-resistant agent, the diffraction intensity ratio [A60°C] / [A25°C] of the maximum peak intensity [A25°C] at a measurement temperature of 25°C to the maximum peak intensity [A60°C] at a measurement temperature of 60°C in a 2θ range of 15° to 30° is 0.3 or more. [Item 11] The oil-resistant agent according to any one of Items 2 to 10, wherein the integral value ratio [integral value B] / [integral value A] is 9.5 to 12, and the diffraction intensity ratio [A60°C] / [A25°C] is 0.5 to 0.9.[Item 12] The oil-proofing agent according to any one of Items 1 to 11, which is used for pulp products. [Item 13] The oil-proofing agent according to Item 12, wherein the pulp product is a food contact product. [Item 14] The oil-proofing agent according to Item 12 or 13, wherein the oil-proofing agent is for internal addition. [Item 15] A pulp composition comprising the oil-proofing agent according to any one of Items 1 to 14 and a pulp base material. [Item 16] A pulp product obtained by treating a pulp base material with the oil-proofing agent according to any one of Items 1 to 14. [Item 17] A method for producing a pulp product, which comprises a step of treating a pulp base material with the oil-proofing agent according to any one of Items 1 to 14.

[0007] According to the present disclosure, oil resistance can be imparted to a substrate (particularly a pulp substrate).

[0008] <Repellent (Oil-Resistant Agent)> The repellent agent in the present disclosure adheres to a substrate (particularly a pulp substrate) and can impart liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or stain resistance, to the substrate, and can also function as a water-resistant agent, oil-resistant agent, water repellent, oil repellent, and / or stain resistance. The repellent agent in the present disclosure is particularly suitable as an oil-resistant agent that imparts oil resistance to the substrate.

[0009] The repellent of the present disclosure contains a wax, particularly a petroleum-based wax (e.g., a hydrocarbon wax), as an active ingredient. The wax may be used as a repellent by itself or in combination with other ingredients as described below.

[0010] The repellent agent in the present disclosure may not contain any compound selected from the group consisting of a compound having a fluoroalkyl group having 8 or more carbon atoms, a compound having a perfluoroalkyl group having 8 or more carbon atoms, a compound having a fluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group, a compound having a fluoroalkyl group, and a compound having a fluorine atom. The repellent agent in the present disclosure can impart liquid repellency to a substrate even if it does not contain these fluorine compounds.

[0011] The volumetric abundance ratio of particles of 100 μm or larger in the repellent agent of the present disclosure, as measured by a laser diffraction scattering method, may be 0.1% or larger, 0.3% or larger, 0.5% or larger, 1% or larger, 1.5% or larger, 3% or larger, 4% or larger, 5% or larger, or 10% or larger, or may be 50% or smaller, 30% or smaller, 20% or smaller, 15% or smaller, 10% or smaller, 5% or smaller, 3% or smaller, or 1.5% or smaller, preferably 20% or smaller, and more preferably 5% or smaller. The method for achieving the volumetric abundance ratio of such particles within the above range is not limited, and may involve, for example, micronizing the particles in the raw material and / or dispersion using a grinder, homogenizer, or the like.

[0012] The volumetric abundance ratio of particles of 10 μm or larger in the composition of the present disclosure, as measured by a laser diffraction scattering method, may be 0.1% or larger, 0.3% or larger, 0.5% or larger, 1% or larger, 1.5% or larger, 3% or larger, 4% or larger, 5% or larger, or 10% or larger, or may be 50% or smaller, 30% or smaller, 20% or smaller, 15% or smaller, 10% or smaller, 5% or smaller, 3% or smaller, or 1.5% or smaller, preferably 30% or smaller, more preferably 15% or smaller. The method for achieving the volumetric abundance ratio of such particles within the above range is not limited, and may be, for example, by using a grinder, homogenizer, or the like to micronize the particles in the raw material and / or dispersion.

[0013] The volume median diameter of the repellent agent of the present disclosure, as measured by a laser diffraction scattering method, 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, or may be 10 μm or less, 5 μm or less, 3 μm or less, 1 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, 0.3 μm or less, or 0.2 μm or less, preferably 1 μm or less, and in one embodiment, 0.01 μm or more and 1 μm or less. In the present disclosure, the volume median diameter refers to the median diameter (D50) in a volume-based particle size distribution measured by a laser diffraction scattering method.

[0014] The average particle size, as determined from a scanning electron microscope image of particles obtained by removing the liquid medium from a water-dispersed composition of the present disclosure (e.g., an oil-resistant agent for pulp) by natural drying at room temperature, 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, or 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 may be micronized using a grinder, homogenizer, or the like. The room temperature is 20°C to 30°C, particularly 25°C.

[0015] The ionic charge density of the repellent of the present disclosure may be -1000 μeq / g or more, -800 μeq / g or more, -600 μeq / g or more, -500 μeq / g or more, -400 μeq / g or more, -250 μeq / g or more, -100 μeq / g or more, -50 μeq / g or more, -25 μeq / g or more, 0 μeq / g or more, 1 μeq / g or more, 25 μeq / g or more, 50 μeq / g or more, 100 μeq / g or more, 200 μeq / g or more, preferably -600 μeq / g or more, for example, -400 μeq / g or more, -200 μeq / g or more, -50 μeq / g or more, or 5000 μeq / g or more. The ionic charge density 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 one preferred embodiment, it may be -600 μeq / g or more and 600 μeq / g or less, particularly -100 μeq / g or more and 100 μeq / g or less. The ionic charge density in the repellent of the present disclosure can be measured, for example, by the following method.

[0016] A sample liquid with a solid content of 0.1 g / L is subjected to anion demand measurement using a particle charge meter (MUTEK PCD-06 manufactured by BTG) using a 1 / 1000 N potassium polyvinyl sulfonate solution, and the ionic charge density (cationic charge density) is calculated using the following formula (1). Alternatively, the cation demand is measured in the same manner using a polydiallyldimethylammonium chloride solution instead of potassium polyvinyl sulfonate, and the ionic charge density (anionic charge density) is calculated using the following formula (1). Ionic charge density (μeq / g) = A / B (1) A: cation demand or anion demand (μeq / L) B: sample liquid concentration (g / L)

[0017] When the composition contains a liquid medium (for example, when the repellent is an aqueous dispersion), in variable-temperature X-ray diffraction measurement of the residue obtained by removing the liquid medium from the repellent, the diffraction intensity ratio [A60°C] / [A25°C] of the maximum peak intensity [A25°C] at a measurement temperature of 25°C to the maximum peak intensity [A60°C] at a measurement temperature of 60°C in the 2θ range of 15° to 30° may be 0.3 or more, 0.4 or more, 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more, or 0.9 or more, preferably 0.5 or more, and may be 1.2 or less, 1.0 or less, 0.9 or less, 0.8 or less, or 0.7 or less, and in one embodiment, 0.3 or more and 1.0 or less, for example, 0.5 or more and 0.9 or less. Repellents with a high diffraction intensity ratio (e.g., above the above-mentioned lower limit) contain a component that has a unique crystalline structure even at 60°C. It is presumed that such a structure enables the effects of the present disclosure to be effectively achieved. Variable temperature X-ray diffraction measurement (XRD-DSC) is performed using Cu Kα radiation as a light source in a nitrogen atmosphere by cooling to -20°C, then raising the temperature to 25°C or 60°C at a rate of 5°C / min, and holding the temperature for 5 minutes before measurement. A RIGAKU SmartLab can be used as the measurement device. The liquid medium is removed from the repellent agent by air-drying it at room temperature and then drying it under reduced pressure for 24 hours.

[0018] [Wax] The repellent of the present disclosure includes wax, particularly hydrocarbon wax. The wax may be an organic substance that is solid at room temperature and becomes liquid when heated, and may be, for example, a hydrocarbon compound or a compound having a hydrocarbon group (e.g., an alkyl group) having 6 to 40 carbon atoms.

[0019] The waxes of the present disclosure can be adhered to a substrate (particularly a pulp substrate) to impart liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or stain resistance to the substrate.

[0020] [Characteristics of Wax, etc.] The characteristics of wax, etc. are shown below.

[0021] The wax may be in a particulate (powder) form. The average particle size of the wax may be 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.2 μm or more, 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, or 0.6 μm or more, and may be 10 μm or less, 5 μm or less, 3 μm or less, 1 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, 0.3 μm or less, or 0.2 μm or less, preferably 1 μm or less. The above particle size is the primary particle size. A particle size within the above range can provide excellent particle stability and good liquid repellency. The average particle size can be measured using a microscope (scanning electron microscope). Specifically, a wax particle sample is observed under a microscope at an arbitrary magnification. Next, if the particle shape is spherical, the diameter is considered to be the particle size, and if the particle shape is non-spherical, the average value of the longest and shortest diameters is considered to be the particle size. By measuring the particle size of all particles present within the field of view, and then moving the field of view and measuring the particle size again, particle sizes are measured at 100 or more points, and the average value is considered to be the average particle size.

[0022] The HD (n-hexadecane) contact angle of the wax may be 10° or more, 20° or more, 25° or more, 30° or more, 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 60° or more, or 65° or more, preferably 25° or more, more preferably 30° or more, and may be 100° or less, 90° or less, or 75° or less. When the wax has an HD contact angle equal to or greater than the above lower limit, it can impart good liquid repellency (particularly oil repellency) to the substrate. The HD contact angle is the static contact angle of the wax with respect to a spin-coated film, and is obtained by dropping 2 μL of HD onto the spin-coated film and measuring the contact angle one second after the drop lands.

[0023] The water contact angle of the wax may be 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 65° or more, 75° or more, 85° or more, 90° or more, or 100° or more, and may be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. When the wax has a water contact angle equal to or greater than the above lower limit, it can impart good liquid repellency (particularly water repellency) to the substrate. The water contact angle is the static contact angle of the wax with respect to a spin-coated film, and is obtained by dropping 2 μL of water on the spin-coated film and measuring the contact angle 1 second after the drop lands.

[0024] The wax may be a low molecular weight (e.g., a molecular weight of 1000 or less, or 500 or less) or a polymer. When the wax is a polymer, its weight average molecular weight may be 1000 or more, 3000 or more, 5000 or more, 7500 or more, 10000 or more, 30000 or more, 100,000 or more, 300,000 or more, or 500,000 or more, or 10,000,000 or less, 7,500,000 or less, 5,000,000 or less, 3,000,000 or less, 1,000,000 or less, 750,000 or less, 500,000 or less, 300,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 3 ...,000 or less, 75000 or less, 50000 or less, or 3,000 or less.

[0025] The melting point of the wax may be 30°C or higher, 40°C or higher, 50°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, particularly preferably 55°C or higher, and may 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, preferably 120°C or lower. The melting point of the wax may be measured in accordance with JIS K 2235-1991. The melting point usually corresponds to the peak top temperature of the endothermic peak with the maximum temperature before melting observed in DSC (differential scanning calorimetry).

[0026] Wax １ The integral ratio [integral B] / [integral A] of the integral of the signal observed in the chemical shift range of 0.79 ppm to 0.93 ppm in the H-NMR spectrum [integral A] to the integral of the signal observed in the chemical shift range of 1.05 ppm to 1.47 ppm [integral B] may be 9 or more, 9.5 or more, 10 or more, 10.5 or more, 11 or more, 11.5 or more, 12 or more, 12.5 or more, 13 or more, 13.5 or more, or 14 or more, preferably 9.5 or more, and may be 25 or less, 22 or less, 20 or less, 18 or less, 16 or less, 14 or less, 13 or less, or 12 or less, and in one aspect is 9 or more to 20 or less, for example, 9.5 or more to 14 or less. In the case of a wax having a high integral ratio, for example, equal to or greater than the above-mentioned lower limit, the proportion of methylene hydrogens present is higher than the proportion of methyl hydrogens present, which may result in a structure with fewer branched hydrocarbon structures. It is believed that such a structure will enable the effects of the present disclosure to be effectively achieved. １ H-NMR measurements are carried out on a solution sample obtained by dissolving the wax in deuterated chloroform.

[0027] In variable-temperature X-ray diffraction measurement of wax, the diffraction intensity ratio [A60°C] / [A25°C] of the maximum peak intensity [A25°C] at a measurement temperature of 25°C to the maximum peak intensity [A60°C] at a measurement temperature of 60°C in the 2θ range of 15° to 30° may be 0.3 or more, 0.4 or more, 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more, or 0.9 or more, preferably 0.5 or more, and may be 1.2 or less, 1.0 or less, 0.9 or less, 0.8 or less, or 0.7 or less, and in one embodiment, 0.3 or more and 1.0 or less, for example, 0.5 or more and 0.9 or less. Waxes with a high diffraction intensity ratio, for example, above the above-mentioned lower limit, have a unique crystalline structure even at 60°C. It is presumed that such a structure enables the effects of the present disclosure to be effectively achieved. Variable temperature X-ray diffraction measurement (XRD-DSC) is performed using Cu Kα radiation as a light source in a nitrogen atmosphere by cooling to −20° C., raising the temperature to 25° C. or 60° C. at a rate of 5° C. / min, and holding the temperature for 5 minutes before measurement. A RIGAKU SmartLab can be used as the measurement device.

[0028] [Types of Wax, etc.] Examples of waxes include mineral waxes (petroleum waxes) such as paraffin wax, microcrystalline wax, montan wax, ozokerite wax, ceresin wax, and petrolatum wax; and synthetic waxes such as Fischer-Tropsch wax, polyethylene wax, and polypropylene wax, and are preferably paraffin wax or microcrystalline wax. The wax in the present disclosure may be a hydrocarbon wax, preferably a chain aliphatic hydrocarbon, for example, a linear or branched hydrocarbon, and particularly a linear hydrocarbon.

[0029] [Amount of Wax] The amount of wax in the repellent may be 0.01% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 50% by weight or more, 70% by weight or more, or 80% by weight or more, and may be 95% 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, 10% by weight or less, 5% by weight or less, or 3% by weight or less. Wax alone may be used as the repellent.

[0030] [Dispersant] The repellent according to the present disclosure may contain a dispersant. The dispersant may be at least one selected from an organic dispersant and an inorganic dispersant. The dispersant may be at least one selected from an anionic dispersant, a nonionic dispersant, a cationic dispersant, an amphoteric dispersant, and an inorganic dispersant.

[0031] As the dispersant, an organic dispersant and an inorganic dispersant may be used individually, or a combination of an organic dispersant and an inorganic dispersant may be used.

[0032] An organic dispersant may be used as the dispersant. The organic dispersant can be classified into a nonionic dispersant, an anionic dispersant, a cationic dispersant, and an amphoteric dispersant, and the organic dispersant may refer to a surfactant.

[0033] The dispersant may be fluorine-free.

[0034] [Nonionic Dispersant] The dispersant may contain a nonionic dispersant, which may be a nonionic surfactant.

[0035] The nonionic dispersant may be a low molecular weight type (e.g., a molecular weight of 2000 or less, particularly 10,000 or less) or a high molecular weight type (e.g., a molecular weight of 2000 or more). The molecular weight of the nonionic dispersant may be 100 or more, 500 or more, 1,000 or more, 2,000 or more, 4,000 or more, or 6,000 or more, or may be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 2,500 or less, 750 or less, or 250 or less.

[0036] Examples of nonionic dispersants include ethers, esters, ester ethers, alkanolamides, polyols and amine oxides.

[0037] An example of an ether is a compound having an oxyalkylene group (preferably a polyoxyethylene group).

[0038] An example of the ester is an ester of an alcohol and a fatty acid. An example of the alcohol is a mono- to trio-hydric (particularly di- to deca-hydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 10 to 30 carbon atoms). An example of the fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0039] An example of an ester ether is a compound in which an alkylene oxide (particularly ethylene oxide) is added to an ester of an alcohol and a fatty acid. An example of an alcohol is a mono- to trio-hydric (particularly di- to deca-hydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms). An example of a fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0040] Examples of alkanolamides are those formed from fatty acids and alkanolamines. The alkanolamides may be monoalkanolamides or dialkanolamines. Examples of fatty acids include saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. The alkanolamines may be alkanols having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, and having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0041] The polyol may be a di- to penta-hydric alcohol having 10 to 30 carbon atoms. The amine oxide may be an oxide (for example, having 5 to 50 carbon atoms) of an amine (secondary amine or preferably tertiary amine).

[0042] The nonionic dispersant is preferably a nonionic dispersant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms in the alkylene group in the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic dispersant is generally preferably 2 to 100.

[0043] 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.

[0044] The nonionic dispersant may be an alkylene oxide adduct of a linear and / or branched aliphatic (saturated and / or unsaturated) group, a polyalkylene glycol ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a sorbitan ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a glycerin ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyglycerin ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a sucrose ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of acetylene glycol, or the like. Among these, those in which the alkylene oxide adduct moiety and the polyalkylene glycol moiety have a structure of 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 have to contain an aromatic group.

[0045] The nonionic dispersant has the formula: １ O-(CH ２ CH２ O) ｐ - (R ２ O) ｑ -R ３ [In the formula, R １ is an alkyl group having 1 to 22 carbon atoms, or an alkenyl group or acyl group having 2 to 22 carbon atoms, ２ are independently the same or different and are alkylene groups having 3 or more carbon atoms (e.g., 3 to 10), ３ is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms, p is a number of 2 or more, and q is a number of 0 or 1 or more.

[0046] R １ R preferably has 8 to 20 carbon atoms, particularly 10 to 18 carbon atoms. １ Preferred specific examples of R include an octyl group, a nonyl group, a trimethylnonyl group, a lauryl group, a tridecyl group, an oleyl group, and a stearyl group. ２ Examples of the nonionic dispersant are a propylene group and a butylene group. In the nonionic dispersant, p may be a number of 3 or more (for example, 5 to 200). q may be a number of 2 or more (for example, 5 to 200). That is, -(R ２ O) ｑ - may form a polyoxyalkylene chain. The nonionic dispersant may be a polyoxyethylene alkylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) at the center. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, and a styrene chain, with the oxypropylene chain being preferred.

[0047] Specific examples of nonionic dispersants include ethylene oxide and hexylphenol, isooctatylphenol, hexadecanol, oleic acid, alkanes (C １２ -C １６ ) thiol, sorbitan mono fatty acid (C ７ -C １９ ) or alkyl (C １２ -C １８) condensation products with amines, etc., sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, lecithin derivatives, etc. Examples of nonionic dispersants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene polyoxybutylene alkyl ethers, polyoxyethylene polyoxypropylene glycol, polyethyleneimine ethoxylate, etc.

[0048] 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, based on the molecular weight of the nonionic dispersant (copolymer). The average molecular weight of the nonionic dispersant is generally 300 to 5,000, for example 500 to 3,000. The nonionic dispersant may be a single type or a mixture of two or more types. The nonionic dispersant may be a mixture of a compound having an HLB (hydrophilic-hydrophobic balance) of less than 15 (particularly 5 or less) and a compound having an HLB of 15 or more. Specifically, it is preferable to select from polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene, and polyoxypropylenes having an HLB value of 1 to 18, and sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene glycerin fatty acid esters, and polyoxyethylene sorbitan fatty acid esters having an HLB value of less than 7.

[0049] [Cationic Dispersant] The dispersant may contain a cationic dispersant. The cationic dispersant may be a cationic surfactant. The cationic dispersant may be a compound having no amide group.

[0050] The cationic dispersant may be a low molecular weight type (e.g., a molecular weight of 2000 or less, particularly 10,000 or less) or a high molecular weight type (e.g., a molecular weight of 2000 or more). The molecular weight of the cationic dispersant may be 100 or more, 500 or more, 1,000 or more, 2,000 or more, 4,000 or more, or 6,000 or more, and may be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 25,000 or less, 50,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 2,500 or less, 750 or less, or 250 or less.

[0051] 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 oxyethylene adduct ammonium salt. Specific examples include amine salt-type dispersants such as alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazolines; quaternary ammonium salt-type dispersants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzalkonium chloride, and benzethonium chloride; and polymer-type cationic dispersants such as Polyquaternium-1 to 47. Examples of cationic dispersants include alkylamine salts and quaternary ammonium salts.

[0052] 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 is hydrogen or a hydrocarbon group having 1 to 40 carbon atoms, and X is an anionic group. ２１ , R ２２ , R ２３ and -R ２４Specific examples of X include alkyl groups (e.g., methyl, butyl, stearyl, and palmityl groups) and aromatic groups (e.g., benzyl and phenyl groups). Specific examples of X include halogens (e.g., chlorine) and acids (e.g., hydrochloric acid and acetic acid). Examples of cationic dispersants include monoalkyltrimethylammonium salts (alkyl having 4 to 40 carbon atoms) and benzalkonium chloride.

[0053] Specifically, the low molecular weight cationic dispersant is represented by the formula: １ ｐ -N ＋ R ２ ｑ X － [In the formula, R １ is C12 or more (e.g. C １２ ~C ５０ ) is a linear and / or branched aliphatic (saturated and / or unsaturated) group of the formula R ２ is H or a C1-4 alkyl group, a benzyl group, a polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (particularly 2, particularly 3) to 50) (CH ３ , C ２ H ５ is particularly preferred), and X is a halogen atom (e.g., chlorine), or C １ ~C ４ or a fatty acid salt of C １ ~C ４ where p is 1 or 2, q is 2 or 3, and p+q=4. １ may have 12 to 50 carbon atoms, for example, 12 to 30 carbon atoms.

[0054] Examples of low molecular weight cationic dispersants include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydropolyoxyethylene)ammonium chloride, benzyldodecyldi(hydropolyoxyethylene)ammonium chloride, N-[2-(diethylamino)ethyl]oleamide hydrochloride, and the like.

[0055] The polymeric cationic dispersant may be any of various polymers (e.g., polyquaternium-1 to -47) having a cationic group (e.g., ammonium group, quaternary ammonium group). Examples of the polymeric cationic dispersant include cationic natural products (particularly cationic sugars) such as cationic starch, cationic cellulose (e.g., O-(2-hydroxy-3-(trimethylammonio)propylhydroxyethylcellulose chloride), cationic guar gum, cationic xanthan gum, and chitosan; and polymers of cationic group-containing monomers such as aziridine, vinylimidazole, aminoalkyl methacrylate, N,N,N',N'-tetramethyl-2-butene-1,4-diamine, quaternized dimethylammonium ethyl methacrylate, diallyldimethylammonium chloride, dimethylaminopropylamine, and quaternized vinylimidazole.

[0056] [Anionic Dispersant] The dispersant may contain an anionic dispersant. The anionic dispersant may be an anionic surfactant. The dispersant may not contain an anionic dispersant.

[0057] The anionic dispersant may be a low molecular weight type (e.g., a molecular weight of 2000 or less, particularly 10,000 or less) or a high molecular weight type (e.g., a molecular weight of 2000 or more). The molecular weight of the anionic dispersant may be 100 or more, 500 or more, 1,000 or more, 2,000 or more, 4,000 or more, or 6,000 or more, and may be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 25,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 2,500 or less, 750 or less, or 250 or less.

[0058] Examples of anionic dispersants include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkanesulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfonic acid salts, N-acylamino acid type dispersants, phosphate mono- or diester type dispersants, and sulfosuccinate esters. An example of an anionic dispersant is a carboxylate (e.g., a fatty acid salt).

[0059] [Amphoteric Dispersant] The dispersant may contain an amphoteric dispersant, which may be an amphoteric surfactant.

[0060] The amphoteric dispersant may be a low molecular weight type (e.g., molecular weight of 2000 or less, particularly 10,000 or less) or a high molecular weight type (e.g., molecular weight of 2000 or more). The molecular weight of the amphoteric dispersant may be 100 or more, 500 or more, 1,000 or more, 2,000 or more, 4,000 or more, or 6,000 or more, and may be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 25,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 2,500 or less, 750 or less, or 250 or less.

[0061] Examples of amphoteric dispersants include alanines, imidazolinium betaines, amido betaines, and acetic acid betaine, and specific examples include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylamino acetic acid betaine, and fatty acid amidopropyl dimethylamino acetic acid betaine.

[0062] [Inorganic Dispersant] The dispersant may contain an inorganic dispersant.

[0063] The average primary particle size of the inorganic dispersant may be 5 nm or more, 30 nm or more, 100 nm or more, 1 μm or more, 10 μm or more, or 25 μm or more, and may be 100 μm or less, 50 μm or less, 10 μm or less, 1 μm or less, 500 nm or less, or 300 nm or less. The average primary particle size can be measured, for example, by observation with a microscope (scanning electron microscope or transmission electron microscope). The inorganic dispersant may be hydrophilic particles.

[0064] 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.

[0065] [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, relative to 100 parts by weight of wax, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less.

[0066] [Liquid Medium] The repellent agent of the present disclosure may contain a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The repellent agent may be a dispersion or a solution. The repellent agent of the present disclosure is preferably a water dispersion.

[0067] Examples of organic solvents include esters (e.g., esters having 2 to 40 carbon atoms, specifically, ethyl acetate and butyl acetate), ketones (e.g., ketones having 2 to 40 carbon atoms, specifically, methyl ethyl ketone and diisobutyl ketone), alcohols (e.g., alcohols having 1 to 40 carbon atoms, specifically, isopropyl alcohol), aromatic solvents (e.g., toluene and xylene), and petroleum solvents (e.g., alkanes having 5 to 10 carbon atoms, specifically, naphtha and kerosene). The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent may contain a compound having at least one hydroxy group (e.g., alcohol, polyols such as glycol-based solvents, ethers of polyols (e.g., monoethers), etc.). These may be used alone or in combination.

[0068] [Amount of Liquid Medium] The amount of the liquid medium may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 1 part by weight of the wax.

[0069] The amount of water may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, per part by weight of wax.

[0070] 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, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 1 part by weight of wax.

[0071] [Silicone] The repellent agent according to the present disclosure may contain silicone (polyorganosiloxane). By containing silicone, it is possible to obtain good texture and durability in addition to good liquid repellency.

[0072] As the silicone, known silicones can be used, and examples of silicones include polydimethylsiloxane and modified silicones (amino-modified, epoxy-modified silicone, carboxy-modified silicone, methylhydrogen silicone, etc.). The silicone may be a silicone wax having wax-like properties. These may be used alone or in combination of two or more.

[0073] The weight average molecular weight of the silicone may be 1,000 or more, 10,000 or more, or 50,000 or more, and may be 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.

[0074] [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, relative to 100 parts by weight of the wax, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0075] [Organic Acid] The repellent of the present disclosure may contain an organic acid. Known organic acids can be used. Preferred organic acids include carboxylic acids, sulfonic acids, sulfinic acids, etc., with carboxylic acids being particularly preferred. Examples of the carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid, etc., with formic acid or acetic acid being particularly preferred. In the present disclosure, one type of organic acid may be used, or two or more types may be used in combination. For example, formic acid and acetic acid may be used in combination.

[0076] [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, relative to 100 parts by weight of wax, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less. The amount of organic acid may be adjusted so that the pH of the repellent is 3 to 10, for example, 5 to 9, particularly 6 to 8. The repellent may be acidic (pH 7 or less, for example, 6 or less).

[0077] [Inorganic Acid] The repellent of the present disclosure may contain an inorganic acid. Known inorganic acids can be used. Examples of inorganic acids include hydrogen chloride, hydrogen bromide, hydrogen iodide, nitric acid, boric acid, sulfuric acid, and phosphoric acid. In the present disclosure, one type of inorganic acid may be used, or two or more types may be used in combination. Adding an inorganic acid can improve the stability of the aqueous dispersion.

[0078] [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, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of wax. The amount of inorganic acid may be adjusted so that the pH of the repellent is 3 to 10, for example, 5 to 9, particularly 6 to 8. The repellent may be acidic (pH 7 or less, for example, 6 or less).

[0079] [Hardening Agent] The repellent of the present disclosure may contain a hardening agent (an active hydrogen-reactive compound or an active hydrogen-containing compound). When the repellent is for paper (e.g., an oil-proofing agent for paper), it does not need to contain a hardening agent.

[0080] [Other Components] The repellent may contain other components in addition to the above-mentioned components. Examples of other components include polysaccharides, flocculants, retention aids, coagulants, binder resins, anti-slip agents, sizing agents, paper strength agents, fillers, antistatic agents, preservatives, UV absorbers, antibacterial agents, deodorizers, fragrances, etc. These may be used alone or in combination of two or more. In addition to the above components, other components include other water and / or oil repellents, dispersants, texture adjusters, softeners, flame retardants, paint fixatives, wrinkle inhibitors, drying speed adjusters, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity adjusters, UV absorbers, antioxidants, pH adjusters, insect repellents, antifoaming agents, shrinkage inhibitors, anti-wrinkle agents after washing, shape retention agents, drape retention agents, ironing improvers, whitening agents, whitening agents, fabric softening clay, dye transfer inhibitors such as polyvinylpyrrolidone, polymer dispersants, stain release agents, scum dispersants, fluorescent whitening agents such as 4,4-bis(2-sulfostyryl)biphenyl disodium (Tinopal CBS-X manufactured by Ciba Specialty Chemicals), dye fixatives, and anti-fading agents such as 1,4-bis(3-aminopropyl)piperazine. The following may be blended: stain removers; enzymes such as cellulase, amylase, protease, lipase, and keratinase as fiber surface modifiers; foam inhibitors; and agents capable of imparting the texture and functionality of silk, such as moisture absorption and release, such as silk protein powder, surface-modified products, or emulsified dispersions thereof (e.g., K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemicals), hydrolyzed silk liquid (Jomo), Silkgen G Soluble S (Ichimaru Falcos)), stain inhibitors (e.g., nonionic polymer compounds composed of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units (e.g., FR627 manufactured by GOO Chemical Industry Co., Ltd.), SRC-1 manufactured by Clariant Japan, etc.). These may be used alone or in combination of two or more. The components may be appropriately determined depending on the application of the repellent.

[0081] [Amount of Other Components] The amount of each or the total amount of the 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, or 100 parts by weight or more, relative to 100 parts by weight of the wax, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0082] <Pulp Composition> The pulp composition according to the present disclosure includes a wax and a pulp base material. The pulp composition according to the present disclosure may have excellent oil resistance.

[0083] The pulp composition of the present disclosure is obtained by adding a wax to a pulp base material. The pulp composition may be obtained by treating the pulp base material with a repellent containing a wax, and the amount of repellent added and the composition of the repellent may be adjusted so that each component is present in a desired amount. Each component that may be contained in the repellent may be added to the pulp composition as a separate additive.

[0084] The pulp composition of the present disclosure may not contain any compound selected from the group consisting of a compound having a fluoroalkyl group having 8 or more carbon atoms, a compound having a perfluoroalkyl group having 8 or more carbon atoms, a compound having a fluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group, a compound having a fluoroalkyl group, and a compound having a fluorine atom. The pulp composition of the present disclosure can impart liquid repellency to a substrate even without containing these fluorine compounds.

[0085] The pH of the pulp composition may be 3 to 10, for example 5 to 9, particularly 6 to 8, and the amount of each component may be adjusted to achieve such a pH.

[0086] [Pulp Base Material] The pulp composition includes a pulp base material. The pulp base material is made of pulp, and the pulp may be wood pulp, non-wood pulp, recycled paper pulp, or the like.

[0087] [Wood Pulp] Wood pulp includes softwood kraft pulp obtained from species such as Abies and Pinus, and hardwood kraft pulp obtained from species such as Acacia, Eucalyptus, Beech, and Populus (e.g., poplar). Examples of softwood kraft pulp include unbleached softwood kraft pulp (NUKP), bleached softwood pulp (NBKP), semi-bleached softwood kraft pulp (NSBKP), and softwood sulfite pulp. Examples of hardwood kraft pulp include unbleached hardwood kraft pulp (LUKP), bleached hardwood kraft pulp (LBKP), semi-bleached hardwood kraft pulp (LSBKP), and hardwood sulfite pulp. The pulps used may be used alone or in combination. In addition to kraft pulp, there are also softwood kraft pulp and hardwood kraft pulp, as well as mechanical pulps such as stone ground pulp (SGP), pressurized stone ground pulp (PGW), refiner ground pulp (RGP), thermoground pulp (TGP), chemiground pulp (CGP), groundwood pulp (GP), thermomechanical pulp (TMP), etc. Furthermore, waste paper pulp includes disintegrated waste paper pulp, disintegrated and deinked waste paper pulp, or disintegrated, deinked and bleached waste paper pulp, which are produced from brown waste paper, recycled kraft envelope paper, recycled magazine paper, recycled newspaper paper, recycled flyer paper, recycled office paper, recycled corrugated cardboard paper, white recycled paper, Kent recycled paper, imitation recycled paper, recycled land paper, etc.

[0088] [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.

[0089] [Pulp fiber length] From the viewpoint of improving oil resistance, the average fiber length of the pulp is preferably 0.1 mm or more, more preferably 0.3 mm or more, and even more preferably 0.5 mm or more, and from the viewpoint of ease of production, it is preferably 5.0 mm or less, more preferably 4.0 mm or less, even more preferably 3.0 mm or less, particularly preferably 2.0 mm or less, and most preferably 1.2 mm or less.

[0090] [Pulp Fiber Width] 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 is preferably 50 μm or less, more preferably 40 μm or less, even more preferably 30 μm or less.

[0091] [Form of Pulp Base Material] The form of the pulp base material when wax is added may be pulp alone, a pulp slurry, a pulp product, etc. Specific examples include pulps such as bleached or unbleached chemical pulps such as kraft pulp and sulfite pulp, bleached or unbleached high-yield pulps such as groundwood pulp, mechanical pulp, and thermomechanical pulp; pulp slurries containing the above pulps; and pulp products such as paper, paper containers, and pulp molded products.

[0092] [Amount of Pulp Base Material] The amount of the pulp base material in the pulp composition may be 0.1% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 50% by weight or more, 75% by weight or more, or 90% by weight or more, and may be 99% by weight or less, 75% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, 4% by weight or less, or 3% by weight or less. When the pulp composition is prepared by internal addition, the amount of the pulp base material in the pulp composition may be 30% by weight or less, and when the pulp composition is prepared by external addition, the amount of the pulp base material in the pulp composition may be 75% by weight or more.

[0093] The amount of the pulp base material may be 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, 90% by weight or more, 95% by weight or more, or 99% by weight or more in the pulp composition excluding the liquid medium, and may be 99.9% by weight or less, 95% by weight or less, 90% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, or 55% by weight or less.

[0094] [Liquid Medium] The pulp composition may contain a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent, and is typically an aqueous medium, particularly water. The liquid medium may also contain a liquid medium derived from a repellent agent.

[0095] [Amount of Liquid Medium] The amount of the liquid medium in the pulp composition may be 0.1 wt% or more, 0.5 wt% or more, 1 wt% or more, 3 wt% or more, 5 wt% or more, 10 wt% or more, 20 wt% or more, 30 wt% or more, 50 wt% or more, 75 wt% or more, 90 wt% or more, or 95 wt% or more, and may be 99 wt% or less, 75 wt% or less, 50 wt% or less, 40 wt% or less, 30 wt% or less, 20 wt% or less, 10 wt% or less, 5 wt% or less, 4 wt% or less, or 3 wt% or less. Typically, when the pulp composition is prepared by internal addition, the amount of the liquid medium in the pulp composition is 50 wt% or more, particularly 90 wt% or more, and when the pulp composition is prepared by external addition, the amount of the liquid medium in the pulp composition is 30 wt% or less, particularly 10 wt% or less.

[0096] [Wax] The pulp composition contains wax, particularly hydrocarbon wax. For details of the types of wax, please refer to the explanation of wax in the section on repellents.

[0097] [Amount of wax] The amount of wax relative to the pulp base material may be 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more, and is preferably 0.5% by weight or more, and may be 25% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, for example, 15% by weight or less, 5.0% by weight or less, or 3.0% by weight or less.

[0098] The wax may be added to the surface of a pulp substrate (e.g., a pulp product such as paper, a paper container, or a pulp molded product) for external application. The amount of wax contained in the coating layer formed by external application is 0.01 g / m 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 ２or more, or 1.0 g / m ２ or more, and ２ Below, 4.0g / m ２ Below, 3.0g / m ２ Below, 2.0g / m ２ Below, 1.0g / m ２ Below, 0.5g / m ２ Below, 0.3g / m ２ or less, or 0.1 g / m ２ It may be the following:

[0099] [Dispersant] The pulp composition may contain a dispersant. For details of the types of dispersants, the explanation of the dispersant in <Repellent> is incorporated herein by reference.

[0100] [Amount of Dispersant] The amount of dispersant may be 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more, and may be 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, preferably 5.0% by weight or less, more preferably 3.0% by weight or less, based on the pulp base material.

[0101] [Paper Strength Agent] The pulp composition may contain a paper strength agent. Examples of the paper strength agent include polyacrylamide-based paper strength agents such as cationic polyacrylamide, anionic polyacrylamide, and amphoteric polyacrylamide; polysaccharide-based paper strength agents such as starch, enzyme-modified starch, thermochemically modified starch, oxidized starch, esterified starch, etherified starch (e.g., hydroxyethylated starch), aldehyde-modified starch, cationized starch, starch, xanthan gum, karaya gum, welan gum, guar gum, pectin, tamarind gum, carrageenan, chitosan, gum arabic, locust bean gum, cellulose, alginic acid, agar, dextran, cellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, chitin nanofiber, cellulose nanofiber, and pullulan, and modified polysaccharides thereof (e.g., modified polysaccharides into which a hydroxyl group or a cationic group has been introduced); Polyamide-based paper strength agents such as polyamide resins, polyamine resins, polyamide-polyamine resins, polyamide-epichlorohydrin resins, polyamide-polyamine-epichlorohydrin resins, polyamide-polyurea-formaldehyde resins, and epoxidized polyamide resins; urea / melamine-based paper strength agents such as urea resins, melamine resins, urea-formaldehyde resins, and melamine-formaldehyde resins; polyvinyl alcohol-based paper strength agents such as polyvinyl alcohol, fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, cation-modified polyvinyl alcohol, and terminally alkyl-modified polyvinyl alcohol; 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. The paper strength agent in the present disclosure is preferably a polyacrylamide-based paper strength agent, a polysaccharide-based paper strength agent, or a polyamide-based paper strength agent.

[0102] [Amount of Paper Strength Agent] The amount of the paper strength agent may be 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more, and may be 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, and is preferably 5.0% by weight or less, based on the pulp.

[0103] [Sizing Agent] The pulp composition may contain a sizing agent. Examples of the sizing agent include cationic sizing agents, anionic sizing agents, neutral sizing agents, and amphoteric sizing agents, such as rosin-based sizing agents (e.g., acidic rosin-based sizing agents, neutral rosin-based sizing agents), alkyl ketene dimers, and alkenyl succinic anhydrides.

[0104] [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, and may be 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, based on the pulp.

[0105] [Other Additives] In addition to the above, the pulp composition may contain other additives such as known paper co-agents used in the production of pulp products, such as fixing agents (aluminum sulfate, etc.), coagulants / flocculants (polyamine resins, etc.), retention aids (polyacrylamide resins, etc.), organic acids (formic acid, acetic acid, etc.), dyes, slime control agents, and antifoaming agents.

[0106] [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, or 5% by weight or more, and may be 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, 3% by weight or less, or 1% by weight or less, based on the pulp base material.

[0107] <Product Manufacturing Method> The product manufacturing method of the present disclosure may include a step of treating a substrate with the repellent agent of the present disclosure as a treatment agent.

[0108] The substrate to be treated with the treatment agent of the present disclosure is not limited, but is preferably a fibrous substrate, particularly a textile substrate or a pulp substrate, and is particularly preferably a pulp substrate.

[0109] Examples of fiber substrates include natural fibers of animal or plant origin such as cotton, hemp, wool, silk, etc., synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polypropylene, etc., semi-synthetic fibers such as rayon, acetate, etc., inorganic fibers such as glass fiber, carbon fiber, asbestos fiber, etc., or mixtures of these fibers. Fiber products include woven fabrics, knitted fabrics, nonwoven fabrics, cloth in the form of clothing (for example, water-repellent clothing, e.g., raincoats), and carpets, but the treatment may also be applied to fibers, yarns, and intermediate fiber products (for example, slivers or rovings) in a state prior to being made into cloth.

[0110] Substrates that can be treated with the treatment agent of the present disclosure are not limited to fibrous substrates, but also include stone, filters (e.g., electrostatic filters), dust masks, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster.

[0111] When the substrate is glass, the produced glass product may be an optical component. A layer (or film), such as a hard coat layer or an anti-reflection layer, may be formed on the surface (outermost layer) of the glass substrate. The anti-reflection layer may be either a single-layer anti-reflection layer or a multi-layer anti-reflection layer. Examples of inorganic substances that can be used for the anti-reflection layer include SiO ２ , SiO, ZrO ２ , TiO ２ , TiO, Ti ２ O ３ , Ti ２ O ５ , Al ２ O ３ , Ta ２ O５ , CeO ２ , MgO, Y ２ O ３ , SnO ２ , MgF ２ , W.O. ３ These inorganic substances may be used alone or in combination of two or more (for example, as a mixture). When a multi-layer antireflection layer is formed, the outermost layer may contain SiO ２ and / or SiO is preferably used. When the article to be manufactured is an optical glass component for a touch panel, a transparent electrode, for example, a thin film using indium tin oxide (ITO) or indium zinc oxide, may be provided on a portion of the surface of the substrate (glass). Furthermore, the substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomization film layer, a hard coating film layer, a polarizing film, a phase difference film, a liquid crystal display module, or the like, depending on its specific specifications.

[0112] [Method for manufacturing pulp products] The pulp products (paper products) in the present disclosure can be obtained by treating a pulp base material with a repellent containing wax to obtain a pulp composition, and then subjecting the pulp composition to processing steps such as drying, heating, and molding, as necessary.

[0113] The repellent agent of the present disclosure can be applied to a pulp substrate as a treatment agent (particularly a surface treatment agent) by a conventionally known method. The treatment method may involve dispersing and diluting the repellent agent of the present disclosure in an organic solvent or water, as necessary, and applying it to the interior and / or surface of the pulp substrate by a known method such as dip coating, spray coating, or foam coating, followed by drying. The dilution ratio may be varied as appropriate 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 is obtained to which the solid components of the repellent are attached. If necessary, the repellent agent may be applied together with an appropriate crosslinking agent, followed by curing.

[0114] The repellent agent can be applied to the pulp substrate by any of the known methods for treating a pulp substrate with a liquid. The pulp substrate may be immersed in the repellent agent, the pulp substrate and the repellent agent may be mixed, or the solution may be applied or sprayed onto the pulp substrate. The treated pulp substrate is preferably dried and cured by heating to develop liquid repellency. The heating temperature may be, for example, 100°C to 200°C, 100°C to 170°C, or 100°C to 120°C. In the present disclosure, the heating time may be 5 seconds to 60 minutes, for example, 30 seconds to 3 minutes.

[0115] Pulp substrate treatment methods can include internal treatment methods in which a repellent is added to the pulp substrate (e.g., in the form of pulp slurry) before papermaking, or external treatment methods in which a repellent is applied to the pulp substrate (e.g., pulp product) after papermaking. Examples of internal treatment methods include mixing and immersion, which may include a step of adding a repellent to the pulp slurry and stirring and mixing it. Examples of external treatment methods include spraying, coating, immersion, and foam application, and specific examples include pond-type two-roll size presses, gate-roll type, and rod-metering size presses. The treatment can be either external or internal. For example, when the pulp substrate is paper, the repellent can be applied to the paper, or the solution can be attached or sprayed onto the paper, or the repellent can be mixed with the pulp slurry before papermaking. When the pulp substrate is a fibrous material, treatment methods include padding, immersion, spraying, and coating. Examples of padding treatments include methods using padding devices described on pages 396-397 of "Textile Dyeing and Processing Dictionary" (published by Nikkan Kogyo Shimbun, 1963) and pages 256-260 of "Color Dyeing Chemistry III" (published by Jikkyo Publishing Co., Ltd., 1975). Examples of coating treatments include methods using coating machines described on pages 473-477 of "Dyeing and Finishing Equipment Directory" (published by Sen-sha, 1981). Examples of immersion treatments include methods using batch dyeing machines described on pages 196-247 of "Dyeing and Finishing Equipment Directory" (published by Sen-sha, 1981). Examples of suitable dyeing machines include liquid jet dyeing machines, air jet dyeing machines, drum dyeing machines, winch dyeing machines, washer dyeing machines, and cheese dyeing machines. Examples of spray treatments include methods using air sprayers that spray the treatment solution in a mist using compressed air, and hydraulic atomization air sprayers.

[0116] The treatment method may be an internal addition treatment in which a repellent is added to the pulp slurry before papermaking. The internal addition treatment may include, but is not limited to, one or more of the following steps: adding the repellent to the pulp slurry and stirring and mixing it; suction-dewatering the pulp composition prepared in the above step through a mesh of a predetermined shape to deposit the pulp composition and form a molded pulp product intermediate; and molding and drying the molded pulp product intermediate in a heated mold to obtain a molded pulp product. The treated paper may be briefly dried at room temperature or at an elevated temperature, and then optionally subjected to a heat treatment depending on the paper's properties. 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 particularly may be 80°C to 180°C. Heat treatment within this temperature range can exhibit excellent oil resistance, etc. The internally treated pulp base material may be treated with a repellent by external addition, and further wax or repellent may be attached to the surface.

[0117] The treatment method may be an external addition treatment in which a repellent agent is applied to the pulp base material after papermaking. Size presses for external addition treatment can also be divided into the following categories based on the application method. One application method is the so-called pond-type two-roll size press, in which a coating liquid (size liquid) is supplied to the nip formed by passing paper between two rubber rolls, creating a coating liquid pool called a pond, and the paper is passed through this coating liquid pool to apply the size liquid to both sides of the paper. Other application methods include the gate roll type, in which the size liquid is applied using a surface transfer method, and the rod metering size press. In the pond-type two-roll size press, the size liquid easily penetrates into the paper, while in the surface transfer type, the size liquid components tend to remain on the paper surface. In the surface transfer type, the coating layer tends to remain on the paper surface compared to the pond-type two-roll size press, and a larger coating layer is formed on the surface than in the pond-type two-roll size press. In the present disclosure, performance can be imparted to paper even when the former pond-type two-roll size press is used. Papers treated in this way may exhibit excellent oil resistance etc., after simple drying at room temperature or at elevated temperatures, optionally followed by a heat treatment which may range in temperature up to 300°C, for example up to 200°C, especially between 80°C and 180°C, depending on the properties of the paper.

[0118] Specific examples of pulp products include paper, paper containers, pulp molded products, food packaging materials, food containers, gypsum board base paper, coated base paper, medium-quality paper, general liners and corrugating media, neutral white roll paper, neutral liners, rust-proof liners and metal interleaving paper, kraft paper, neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper, and neutral information paper, etc. Suitable examples of pulp products include food packaging materials and food containers, such as pulp products for food contact applications, particularly pulp molded products for food contact applications.

[0119] Although the embodiments have been described above, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims.

[0120] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to these examples.

[0121] The test procedure is as follows:

[0122] [Volume abundance ratio of particles of 10 μm or more] The abundance ratio of particles of 10 μm or more was calculated from the volume-based frequency distribution (volume distribution) obtained by measuring the water-dispersible oil-resistant agent using a laser diffraction / scattering device, and this value was used as the volume abundance ratio of particles of 10 μm or more.

[0123] [Volume abundance ratio of particles of 100 μm or more] The abundance ratio of particles of 100 μm or more was calculated from the volume-based frequency distribution (volume distribution) obtained by measuring the water-dispersible oil-resistant agent using a laser diffraction / scattering device, and this value was taken as the volume abundance ratio of particles of 100 μm or more.

[0124] [Median diameter D50] The median diameter D50 was determined by measuring the water-dispersible oil-resistant agent using a laser diffraction / scattering device.

[0125] [Ionic Charge Density] The ionic charge density of the oil-proofing agent of the present disclosure can be measured, for example, by the following method. A sample liquid having a solids content of 0.1 g / L is subjected to measurement of anionic demand using a particle charge meter (MUTEK PCD-04 manufactured by BTG) using a 1 / 1000 N potassium polyvinyl sulfonate solution, and the ionic charge density (cationic charge density) is calculated using the following formula (1). Alternatively, a polydiallyldimethylammonium chloride solution is used instead of potassium polyvinyl sulfonate to similarly measure cation demand, and the ionic charge density (anionic charge density) is calculated using the following formula (1). Ionic charge density (μeq / g) = A / B (1), where A: cation demand or anionic demand (μeq / L), B: sample liquid concentration (g / L).

[0126] [Preparation of Pulp Mold] Pulp mold was molded using an automatic molding machine. A mesh-like body was placed on a metal pulp mold mold with multiple suction holes at the bottom, and a metal tank was placed on top. A mixture of pulp slurry and water-dispersible oil-proofing agent was placed in the upper metal tank. A vacuum pump was used to suck and dehydrate the pulp-containing aqueous composition through the pulp mold mold and mesh-like body from the side opposite the side where the mesh-like body was placed in the pulp mold mold, and the solids (pulp, etc.) contained in the pulp-containing aqueous composition were deposited on the mesh-like body to obtain a pulp mold intermediate. Next, the obtained pulp mold intermediate was dried from above and below in a metal male-female mold heated to 60 to 250°C under a pressure of 0.05 to 5 MPa. This produced a pulp molded product molded into the shape of a container.

[0127] [Practical oil resistance test at 65°C] The pulp mold was pretreated by storing it under conditions of 23°C and 50% humidity for 12 hours. 100 ml of corn oil at 65°C was poured into the pulp mold, and after leaving it at room temperature for 45 minutes, the corn oil was removed from the pulp mold and the degree of oil staining of the pulp mold was evaluated. The following evaluation values ​​were set depending on the degree of staining: 5: No staining on the inside 4: Stained on the inside. No staining on the backside 3: Stained on the inside. Slight staining on the backside 2: Stained on the inside. Staining on the backside was less than 50% of the area 1: Stained on the inside. Staining on the backside was 50% or more but less than 100% of the area 0: Stained on the entire backside

[0128] [Differential Scanning Calorimetry of Wax] The maximum endothermic peak temperature, melting point, crystallization temperature, and glass transition temperature of the wax were calculated by differential scanning calorimetry (DSC). DSC measurement was performed by cooling to -20°C under a nitrogen atmosphere, and then measuring the endothermic peak observed during the subsequent temperature increase to 180°C at 10°C / min. When multiple endothermic peaks appeared, the endothermic peak with the highest temperature was taken as the maximum endothermic peak, and the top of this peak was taken as the maximum endothermic peak temperature. This maximum endothermic peak temperature corresponds to the melting point of the wax. The endothermic heat was calculated by calculating the heat quantity within a range of ±10°C of the endothermic peak temperature.

[0129] [Variable Temperature X-ray Diffraction Measurement of Wax] The crystalline state of the wax was measured by X-ray diffraction (XRD) using a RIGAKU SmartLab. Cu Kα radiation was used as the light source. Variable temperature XRD (XRD-DSC) measurements were performed under a nitrogen atmosphere by cooling to -20°C, then heating to 25°C or 60°C at a rate of 5°C / min, and holding for 5 minutes before measurement. The half-width of the peak was defined as the 2θ width of the peak at half the intensity between the baseline and the peak top. The diffraction intensity ratio [A60°C / A25°C] was calculated as follows: The intensity of the maximum point of the diffraction intensity in the 2θ range of 15° to 30° at a measurement temperature of 25°C was defined as [Peak Intensity A25°C]. The intensity of the maximum point of the diffraction intensity in the 2θ range of 15° to 30° at a measurement temperature of 60°C was defined as [Peak Intensity A60°C]. The diffraction intensity ratio [A60°C / A25°C] was calculated by dividing [peak intensity A60°C] by [peak intensity A25°C] according to the following formula: Diffraction intensity ratio [A60°C / A25°C] = [peak intensity A60°C] / [peak intensity A25°C]

[0130] [Wax １ H-NMR spectrum measurement] of wax １ The integral ratio [integral B] / [integral A] of the integral of the signal observed in the chemical shift range of 0.79 ppm to 0.93 ppm in the H-NMR spectrum [integral A] to the integral of the signal observed in the chemical shift range of 1.05 ppm to 1.47 ppm [integral B] was measured by the following method. The wax was dissolved in deuterated chloroform (containing tetramethylsilane) to prepare a measurement sample. Then, using a nuclear magnetic resonance spectrometer (JEOL 400 MHz), １H-NMR spectra were measured. The chemical shift reference was set so that the peak of tetramethylsilane (TMS) was at 0 ppm in the obtained spectrum. First-order phase correction was performed in the chemical shift region of TMS, and second-order phase correction was performed in the chemical shift region of deuterated chloroform to adjust the signal flatness. The integral value of the signal in the chemical shift range of 0.79 ppm to 0.93 ppm was calculated, and this integral value was set to 6, which was designated as [integral value A]. Next, the integral value of the signal observed in the chemical shift range of 1.05 ppm to 1.47 ppm or less was calculated, which was designated as [integral value B]. [integral value B] was divided by [integral value A] to calculate [integral value B] / [integral value A].

[0131] [Differential Scanning Calorimetry of the Solid Component Obtained by Removing the Liquid Medium from the Oil-Resistant Agent] The maximum endothermic peak temperature, melting point, crystallization temperature, and glass transition temperature of the solid component obtained by removing the liquid medium from the oil-resistant agent were calculated by differential scanning calorimetry (DSC). The liquid medium was removed from the oil-resistant agent by natural drying at room temperature, followed by drying under reduced pressure for 24 hours. DSC measurements were performed under a nitrogen atmosphere, with the sample cooled to -20°C and then the endothermic peak observed during the subsequent heating process to 180°C at a rate of 10°C / min. When multiple endothermic peaks appeared, the highest endothermic peak was designated as the maximum endothermic peak, and the top of that peak was designated as the maximum endothermic peak temperature. The endothermic heat was calculated by calculating the heat within a range of ±10°C from the endothermic peak temperature.

[0132] [Variable-Temperature X-ray Diffraction Measurement of the Solid Component Obtained by Removing the Liquid Medium from the Oil-Resistant Agent] The crystalline state of the solid component obtained by removing the liquid medium from the oil-resistant agent was measured by X-ray diffraction (XRD) using a RIGAKU SmartLab. Cu Kα radiation was used as the light source. Variable-temperature XRD (XRD-DSC) measurements were performed under a nitrogen atmosphere by cooling to -20°C, then heating to 25°C or 55°C at a rate of 5°C / min, and holding for 5 minutes before measurement. The half-width of the peak was defined as the 2θ width of the peak at half the intensity between the baseline and the peak top. The diffraction intensity ratio [A55°C / A25°C] was calculated as follows: The intensity of the maximum diffraction intensity in the 2θ range of 15° to 30° at a measurement temperature of 25°C was defined as [Peak Intensity A25°C]. The intensity of the maximum point of the diffraction intensity in the 2θ range of 15° to 30° at a measurement temperature of 60°C was taken as [Peak Intensity A60°C]. The diffraction intensity ratio [A60°C / A25°C] was calculated by dividing [Peak Intensity A60°C] by [Peak Intensity A25°C] according to the following formula: Diffraction Intensity Ratio [A60°C / A25°C] = [Peak Intensity A60°C] / [Peak Intensity A25°C] The liquid medium was removed from the oil-resistant agent by air-drying it at room temperature, followed by drying it under reduced pressure for 24 hours.

[0133] [Evaluation Example 1] Using Paraffin Wax-115 (manufactured by Nippon Seiro Co., Ltd.), Paraffin Wax-120 (manufactured by Nippon Seiro Co., Ltd.), HNP-3 (manufactured by Nippon Seiro Co., Ltd.), HNP-10 (manufactured by Nippon Seiro Co., Ltd.), and HNP-51 (manufactured by Nippon Seiro Co., Ltd.), differential scanning calorimetry, variable temperature X-ray diffraction measurement, and １ H-NMR spectrum measurement was performed. The maximum endothermic peak temperature in differential scanning calorimetry, the peak intensity A25°C at a measurement temperature of 25°C and the peak intensity A60°C at a measurement temperature of 60°C in variable temperature X-ray diffraction measurement, and the diffraction intensity ratio A60°C / A25°C calculated from them, １ The results of the H-NMR spectrum measurement are shown in Table 1.

[0134] Example 1: 2 g of wax (HNP-3, manufactured by Nippon Seiro Co., Ltd.), 0.2 g of polyethylene oxide alkyl ether (alkyl carbon number 6 to 16, HLB: 7), and 17.8 g of water were mixed to obtain an aqueous dispersion. This aqueous dispersion was heated to 85°C and then treated with an ultrasonic homogenizer for 20 minutes to obtain a water-dispersed oil-proofing agent. The obtained water-dispersed oil-proofing agent exhibited the following properties: Median diameter D50: 0.9 μm, Volume fraction of particles 100 μm or larger: 0%, Volume fraction of particles 10 μm or larger: 9%, Charge density: 21 μeq / g. The water-dispersed oil-proofing agent was added to a 0.5 wt% aqueous pulp slurry to give a ratio of 5 wt% of the pulp in terms of solids content, to prepare a pulp composition. The pulp-containing water-dispersed oil-proofing agent was placed in an automatic molding machine to produce a pulp mold. When the pulp mold was subjected to a practical oil resistance test at 65°C, it scored 4 points. In addition, the solid component obtained by removing the liquid medium from the water-dispersible oil-proofing agent was subjected to variable temperature X-ray diffraction measurement, and the results are shown in Table 2.

[0135] Example 2: 2 g of wax (HNP-10, manufactured by Nippon Seiro Co., Ltd.), 0.2 g of polyethylene oxide alkyl ether (alkyl carbon number 6 to 16, HLB: 7), and 17.8 g of water were mixed to obtain an aqueous dispersion. This aqueous dispersion was heated to 85°C and then treated with an ultrasonic homogenizer for 20 minutes to obtain a water-dispersed oil-proofing agent. The obtained water-dispersed oil-proofing agent exhibited the following properties: Median diameter D50: 0.9 μm, Volume fraction of particles 100 μm or larger: 0%, Volume fraction of particles 10 μm or larger: 11%, Charge density: 19 μeq / g. The water-dispersed oil-proofing agent was added to a 0.5 wt% aqueous pulp slurry to give a ratio of 5 wt% of the pulp in terms of solids content, to prepare a pulp composition. The pulp-containing water-dispersed oil-proofing agent was placed in an automatic molding machine to produce a pulp mold. When the pulp mold was subjected to a practical oil resistance test at 65°C, it scored 4 points. In addition, the solid component obtained by removing the liquid medium from the water-dispersible oil-proofing agent was subjected to variable temperature X-ray diffraction measurement, and the results are shown in Table 2.

[0136] Example 3: 2 g of HNP-51 wax (manufactured by Nippon Seiro Co., Ltd.), 0.2 g of polyethylene oxide alkyl ether (alkyl carbon number 6 to 16, HLB: 7), and 17.8 g of water were mixed to obtain an aqueous dispersion. This aqueous dispersion was heated to 85°C and then treated with an ultrasonic homogenizer for 20 minutes to obtain a water-dispersed oil-proofing agent. The obtained water-dispersed oil-proofing agent exhibited the following properties: Median diameter D50: 0.8 μm, Volume fraction of particles 100 μm or larger: 0%, Volume fraction of particles 10 μm or larger: 12%, Charge density: 25 μeq / g. The water-dispersed oil-proofing agent was added to a 0.5 wt% aqueous pulp slurry to give a ratio of 5 wt% of the pulp in terms of solids content, to prepare a pulp composition. The pulp-containing water-dispersed oil-proofing agent was placed in an automatic molding machine to produce a pulp mold. When the pulp mold was subjected to a practical oil resistance test at 65°C, it scored 4 points. In addition, the solid component obtained by removing the liquid medium from the water-dispersible oil-proofing agent was subjected to variable temperature X-ray diffraction measurement, and the results are shown in Table 2.

[0137] Example 4 2 g of HNP-51 wax (manufactured by Nippon Seiro Co., Ltd.), 0.18 g of benzalkonium chloride, and 17.8 g of water were mixed to obtain an aqueous dispersion. This aqueous dispersion was heated to 85°C and then treated with an ultrasonic homogenizer for 20 minutes to obtain a water-dispersed oil-proofing agent. The obtained water-dispersed oil-proofing agent exhibited the following properties: Median diameter D50: 0.75 μm Volume ratio of particles 100 μm or larger: 0% Volume ratio of particles 10 μm or larger: 5% Charge density: 80 μeq / g The water-dispersed oil-proofing agent was added to an aqueous pulp slurry with a concentration of 0.5 wt% to give a ratio of 5 wt% relative to the pulp in terms of solids content, to prepare a pulp composition. The pulp-containing water-dispersed oil-proofing agent was placed in an automatic molding machine to produce a pulp mold. The pulp mold was subjected to a practical oil resistance test at 65°C, scoring 4 points. Furthermore, the solid component obtained by removing the liquid medium from the water-dispersible oil-proofing agent was subjected to variable temperature X-ray diffraction measurement, and the results are shown in Table 2.

[0138] Example 5 2 g of HNP-51 wax (manufactured by Nippon Seiro Co., Ltd.), 0.05 g of cationic starch, 0.04 g of an abietic acid derivative (rosin-based sizing agent), 0.04 g of formic acid, 0.04 g of acetic acid, and 7.83 g of water were mixed, heated to 95°C, and then treated with an ultrasonic homogenizer for 20 minutes to obtain a water-dispersible oil-proofing agent. The obtained water-dispersible oil-proofing agent exhibited the following properties: Median diameter D50: 0.6 μm Volume fraction of particles of 100 μm or larger: 0% Volume fraction of particles of 10 μm or larger: 0.4% Charge density: 16 μeq / g Using the obtained water-dispersible oil-proofing agent, a pulp composition was prepared in the same manner as in Example 1, and a pulp mold was produced. The pulp mold was subjected to a practical oil resistance test at 65°C, scoring 4 points. Furthermore, the solid component obtained by removing the liquid medium from the water-dispersible oil-proofing agent was subjected to variable temperature X-ray diffraction measurement, and the results are shown in Table 2.

[0139] Example 6 2 g of HNP-51 wax (manufactured by Nippon Seiro Co., Ltd.), 0.10 g of cationic starch, 0.04 g of an abietic acid derivative (rosin-based sizing agent), 0.02 g of formic acid, 0.02 g of acetic acid, and 7.87 g of water were mixed, heated to 95°C, and then treated with an ultrasonic homogenizer for 20 minutes to obtain a water-dispersible oil-proofing agent. The obtained water-dispersible oil-proofing agent exhibited the following properties: Median diameter D50: 0.26 μm Volume fraction of particles of 100 μm or larger: 0% Volume fraction of particles of 10 μm or larger: 0.1% Charge density: 39 μeq / g Using the obtained water-dispersible oil-proofing agent, a pulp composition was prepared in the same manner as in Example 1, and a pulp mold was produced. The pulp mold was subjected to a practical oil resistance test at 65°C, scoring 4 points.

[0140] Comparative Example 1: 2 g of Paraffin Wax-115 wax (manufactured by Nippon Seiro Co., Ltd.), 0.2 g of polyethylene oxide alkyl ether (alkyl carbon number 6 to 16, HLB: 7), and 17.8 g of water were mixed to obtain an aqueous dispersion. This aqueous dispersion was heated to 85°C and then treated with an ultrasonic homogenizer for 20 minutes to obtain a water-dispersed oil-proofing agent. The obtained water-dispersed oil-proofing agent exhibited the following properties: Median diameter D50: 0.9 μm, Volume fraction of particles 100 μm or larger: 0%, Volume fraction of particles 10 μm or larger: 10%, Charge density: 22 μeq / g. The water-dispersed oil-proofing agent was added to a 0.5 wt% aqueous pulp slurry to give a ratio of 5 wt% of the pulp in terms of solids content, to prepare a pulp composition. The pulp-containing water-dispersed oil-proofing agent was placed in an automatic molding machine to produce a pulp mold. When the pulp mold was subjected to a practical oil resistance test at 65° C., it received a score of 0. Furthermore, the solid component obtained by removing the liquid medium from the water-dispersible oil-proofing agent was subjected to variable-temperature X-ray diffraction measurement, and the results are shown in Table 2.

[0141] Comparative Example 2: 2 g of Paraffin Wax-120 (manufactured by Nippon Seiro Co., Ltd.) wax, 0.2 g of polyethylene oxide alkyl ether (alkyl carbon number 6 to 16, HLB: 7), and 17.8 g of water were mixed to obtain an aqueous dispersion. This aqueous dispersion was heated to 85°C and then treated with an ultrasonic homogenizer for 20 minutes to obtain a water-dispersed oil-proofing agent. The obtained water-dispersed oil-proofing agent exhibited the following properties: Median diameter D50: 0.9 μm, Volume fraction of particles 100 μm or larger: 0%, Volume fraction of particles 10 μm or larger: 11%, Charge density: 21 μeq / g. The water-dispersed oil-proofing agent was added to a 0.5 wt% aqueous pulp slurry to give a ratio of 5 wt% of the pulp in terms of solids content, to prepare a pulp composition. The pulp-containing water-dispersed oil-proofing agent was placed in an automatic molding machine to produce a pulp mold. When the pulp mold was subjected to a practical oil resistance test at 65° C., it received a score of 0. Furthermore, the solid component obtained by removing the liquid medium from the water-dispersible oil-proofing agent was subjected to variable-temperature X-ray diffraction measurement, and the results are shown in Table 2.

Claims

1. An oil-resistant agent containing wax, wherein the １ Integral value ratio [Integral value B] / [Integral value A] of the integral value [Integral value A] of the signal observed in the range of chemical shift of 0.79 ppm or more and 0.93 ppm or less and the integral value [Integral value B] of the signal observed in the range of chemical shift of 1.05 ppm or more and 1.47 ppm or less in the 1H-NMR spectrum is 9 or more.

2. In the temperature-variable X-ray diffraction measurement of the wax, the diffraction intensity ratio [A60°C] / [A25°C] of the maximum peak intensity [A25°C] at the measurement temperature of 25°C and the maximum peak intensity [A60°C] at the measurement temperature of 60°C in the region where 2θ is 15° or more and 30° or less is 0.3 or more. The oil-resistant agent according to claim 1.

3. The wax is a petroleum wax. The oil-resistant agent according to claim 1 or 2.

4. The wax is at least one selected from the group consisting of paraffin wax and microcrystalline wax. The oil-resistant agent according to any one of claims 1 to 3.

5. The melting point of the wax is 55°C or more. The oil-resistant agent according to any one of claims 1 to 4.

6. The oil-resistant agent is an aqueous dispersion. The oil-resistant agent according to any one of claims 1 to 5.

7. The oil-resistant agent contains a dispersant, and the dispersant is at least one selected from the group consisting of a nonionic dispersant, an anionic dispersant, and a cationic dispersant. The oil-resistant agent according to any one of claims 1 to 6.

8. The oil-resistant agent is an aqueous dispersion, the oil-resistant agent contains a dispersant, and the volume median diameter (D50) measured by the laser diffraction scattering method of the oil-resistant agent is 0.01 μm or more and 1 μm or less. The oil-resistant agent according to any one of claims 1 to 7.

9. The charge density is -600 μeq / g or more and 600 μeq / g or less. The oil-resistant agent according to any one of claims 1 to 8.

10. The oil-resistant agent contains a liquid medium, and in the temperature-variable X-ray diffraction measurement of the residue obtained by removing the liquid medium from the oil-resistant agent, the diffraction intensity ratio [A60°C] / [A25°C] of the maximum peak intensity [A25°C] at the measurement temperature of 25°C and the maximum peak intensity [A60°C] at the measurement temperature of 60°C in the region where 2θ is 15° or more and 30° or less is 0.3 or more. The oil-resistant agent according to any one of claims 1 to 9.

11. The integral value ratio [integral value B] / [integral value A] is 9.5 or more and 12 or less, and the diffraction intensity ratio [A60°C] / [A25°C] is 0.5 or more and 0.9 or less. The oil-resistant agent according to any one of claims 2 to 10.

12. It is for pulp products. The oil-resistant agent according to any one of claims 1 to 11.

13. The pulp product is a product for food contact. The oil-resistant agent according to claim 12.

14. The oil-resistant agent is for internal addition. The oil-resistant agent according to claim 12 or 13.

15. A pulp composition containing the oil-resistant agent according to any one of claims 1 to 14 and a pulp base material.

16. A pulp product obtained by treating a pulp base material with the oil-resistant agent according to any one of claims 1 to 14.

17. A method for manufacturing a pulp product, comprising a step of treating a pulp base material with the oil-resistant agent according to any one of claims 1 to 14.

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