Agent for imparting oil resistance

Abstract

To provide a novel agent for imparting oil resistance, which is capable of imparting oil resistance to a base material, particularly a pulp base material.SOLUTION: 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.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a sizing agent, particularly an oil-resistant agent.

Background Art

[0002] Patent Document 1 discloses a paper base material for a deoxygenation packaging material containing a wax having a melting point of 50°C or higher and 80°C or lower.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] Patent Document 1 1 does not describe or suggest an oil-resistant agent containing a wax having specific chemical shift values in an H-NMR spectrum and / or specific peak intensities in temperature variable X-ray diffraction measurements.

[0005] An object of the present disclosure is to provide a novel oil-resistant agent capable of imparting oil resistance to a base material (particularly a pulp base material).

Means for Solving the Problems

[0006] The present disclosure includes the following aspects: [Item 1] An oil-resistant agent containing a wax, wherein the 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 H-NMR spectrum of the wax is 9 or more. 1 The oil-resistant agent. [Item 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. [Claim 3] The oil-resistant agent according to claim 1 or 2, wherein the wax is a petroleum wax. [Claim 4] The oil-resistant agent according to any one of claims 1 to 3, wherein the wax is at least one selected from the group consisting of paraffin wax and microcrystalline wax. [Claim 5] The oil-resistant agent according to any one of claims 1 to 4, wherein the melting point of the wax is 55°C or more. [Claim 6] The oil-resistant agent according to any one of claims 1 to 5, wherein the oil-resistant agent is an aqueous dispersion. [Claim 7] The oil-resistant agent contains a dispersant, The oil-resistant agent according to any one of claims 1 to 6, wherein the dispersant is at least one selected from the group consisting of a nonionic dispersant, an anionic dispersant, and a cationic dispersant. [Claim 8] The oil-resistant agent is an aqueous dispersion, The oil-resistant agent contains a dispersant, The oil-resistant agent according to any one of claims 1 to 7, wherein 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. [Claim 9] The oil-resistant agent according to any one of claims 1 to 8, wherein the charge density is -600 μeq / g or more and 600 μeq / g or less. [Claim 10] The oil-resistant agent contains a liquid medium, 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. [Item 11] An oil-resistant agent according to any one of Items 1 to 10, which is for pulp products. [Item 12] The oil-resistant agent according to Item 11, wherein the pulp product is a product for food contact. [Item 13] The oil-resistant agent according to Item 11 or 12, wherein the oil-resistant agent is for internal addition. [Item 14] A pulp composition comprising an oil-resistant agent according to any one of Items 1 to 13 and a pulp base material. [Item 15] A pulp product obtained by treating a pulp base material with an oil-resistant agent according to any one of Items 1 to 13. [Item 16] A method for producing a pulp product, comprising a step of treating a pulp base material with an oil-resistant agent according to any one of Items 1 to 13. [Advantages of the Invention]

[0007] According to the present disclosure, oil resistance can be imparted to a base material (particularly a pulp base material). [Modes for Carrying Out the Invention]

[0008] [Repellent (Oil-Resistant Agent)] The repellent in the present disclosure adheres to a base material (particularly a pulp base material) and can impart liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or antifouling property, to the base material, and can also function as a water-resistant agent, an oil-resistant agent, a water-repellent agent, an oil-repellent agent, and / or an antifouling agent. The repellent in the present disclosure is particularly suitable as an oil-resistant agent for imparting oil resistance to a base material.

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

[0010] The repellent in the present disclosure may not have any selected from the group consisting of a compound having a fluoroalkyl group with 8 or more carbon atoms, a compound having a perfluoroalkyl group with 8 or more carbon atoms, a compound having a fluoroalkyl group with 4 or more carbon atoms, a compound having a perfluoroalkyl group with 4 or more carbon atoms, a compound having a perfluoroalkyl group, a compound having a fluoroalkyl group, and a compound having a fluorine atom. The repellent in the present disclosure can impart liquid repellency to the substrate even without containing these fluorine compounds.

[0011] The volume occupancy ratio of particles of 100 μm or more measured by the laser diffraction scattering method in the repellent of the present disclosure may be 0.1% or more, 0.3% or more, 0.5% or more, 1% or more, 1.5% or more, 3% or more, 4% or more, 5% or more, or 10% or more, and may also be 50% or less, 30% or less, 20% or less, 15% or less, 10% or less, 5% or less, 3% or less, or 1.5% or less. Preferably, it is 20% or less, and more preferably 5% or less. The method for setting the volume occupancy ratio of such particles within the above range is not limited. For example, a pulverizer, a homogenizer, or the like can be used to refine the particles in the raw material and / or the dispersion.

[0012] The volume occupancy ratio of particles of 10 μm or more measured by the laser diffraction scattering method in the composition of the present disclosure may be 0.1% or more, 0.3% or more, 0.5% or more, 1% or more, 1.5% or more, 3% or more, 4% or more, 5% or more, or 10% or more, and may also be 50% or less, 30% or less, 20% or less, 15% or less, 10% or less, 5% or less, 3% or less, or 1.5% or less. Preferably, it is 30% or less, and more preferably 15% or less. The method for setting the volume occupancy ratio of such particles within the above range is not limited. For example, a pulverizer, a homogenizer, or the like can be used to refine the particles in the raw material and / or the dispersion.

[0013] The volume median diameter measured by the laser diffraction scattering method in the water repellent of the present disclosure may be 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.2 μm or more, 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, or 0.6 μm or more, and may also be 10 μm or less, 5 μm or less, 3 μm or less, 1 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, 0.3 μm or less, or 0.2 μm or less, preferably 1 μm or less, and in one aspect is 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 the volume-based particle size distribution by the laser diffraction scattering method.

[0014] The average particle diameter obtained from the observation image of a scanning electron microscope of particles obtained by removing the liquid medium by natural drying at room temperature from a water repellent (for example, an oil-resistant agent for pulp), which is a water-dispersible composition of the present disclosure, may be 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.2 μm or more, 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, or 0.6 μm or more, and may also be 10 μm or less, 5 μm or less, 3 μm or less, 1 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, 0.3 μm or less, or 0.2 μm or less, preferably 1 μm or less. To obtain a particle diameter within the above range, for example, a pulverizer, a homogenizer, or the like may be used to refine the particles in the raw material and / or the dispersion liquid. Note that room temperature is 20°C to 30°C, particularly 25°C.

[0015] The ionic charge density in the sizing agent 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, and may also be 5000 μeq / g or less, 2500 μeq / g or less, 1000 μeq / g or less, 750 μeq / g or less, 600 μeq / g or less, 500 μeq / g or less, 400 μeq / g or less, 350 μeq / g or less, 300 μeq / g or less, 200 μeq / g or less, 100 μeq / g or less, or 50 μeq / g or less, preferably 1000 μeq / g or less, more preferably 500 μeq / g or less, for example 300 μeq / g or less, particularly 100 μeq / g or less, and in a preferred embodiment 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 sizing agent of the present disclosure can be measured, for example, by the following method.

[0016] Measure the anion demand of a sample solution with a solid content of 0.1 g / L using a 1 / 1000 normal potassium polyvinyl sulfonate solution with a particle charge meter (MUTEK PCD-06 manufactured by BTG), and calculate the ionic charge density (cation charge density) from the following formula (1). Alternatively, measure the cation demand in the same manner using a poly(diallyldimethylammonium chloride) solution instead of potassium polyvinyl sulfonate, and calculate the ionic charge density (anion charge density) from the following formula (1). Ionic charge density (μeq / g) = A / B (1) A: Cation demand or anion demand (μeq / L) B: Sample solution concentration (g / L)

[0017] When the composition contains a liquid medium (for example, when the repellent is an aqueous dispersion), in the temperature variable 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 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 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 also be 1.2 or less, 1.0 or less, 0.9 or less, 0.8 or less, or 0.7 or less. In one embodiment, it is 0.3 or more and 1.0 or less, for example, 0.5 or more and 0.9 or less. In the case of a repellent with a high diffraction intensity ratio (for example, not less than the above lower limit value), it contains a component having a specific crystal structure even at 60°C. With such a structure, it is presumed that the effects of the present disclosure can be achieved well. The measurement of the temperature variable X-ray diffraction measurement, the temperature variable XRD (XRD-DSC) measurement, is performed by using the Kα line of Cu as the light source, cooling to -20°C under a nitrogen atmosphere, then heating to 25°C or 60°C at a rate of 5°C / min, holding for 5 minutes, and then measuring. As the measuring device, SmartLab of RIGAKU can be used. Also, the removal of the liquid medium from the repellent is carried out by natural drying at room temperature and then drying under reduced pressure for 24 hours.

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

[0019] The wax in the present disclosure can adhere to a substrate (particularly a pulp substrate) and impart liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or antifouling property to the substrate.

[0020] [Properties of Wax, etc.] The properties of the wax, etc. are shown below.

[0021] The wax may be in particulate form (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 also be 10 μm or less, 5 μm or less, 3 μm or less, 1 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, 0.3 μm or less, or 0.2 μm or less, preferably 1 μm or less. The above particle size is the primary particle size. By being within the above range, excellent particle stability can be achieved, and liquid repellency can be improved. The average particle size can be measured with a microscope (scanning electron microscope). Specifically, a particle sample of the wax is observed with a microscope at an arbitrary magnification. Next, when the particle shape is spherical, its diameter, and when it is non-spherical, the average value of the longest diameter and the shortest diameter are regarded as the particle size. The particle sizes of all the particles present in the field of view are measured, and the process of moving the field of view and measuring the particle size again is repeated to measure the particle size at 100 points or more, and the average value thereof is taken as 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 also be 100° or less, 90° or less, or 75° or less. By having an HD contact angle of the above lower limit or more, good liquid repellency (especially oil repellency) can be imparted to the substrate. The HD contact angle refers to the static contact angle with respect to the spin-coated film of the wax, and is obtained by dropping 2 μL of HD onto the spin-coated film and measuring the contact angle 1 second after droplet landing.

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

[0024] The wax may be a low molecule (for example, having a molecular weight of 1000 or less, or 500 or less), or may be a high molecule. When the wax is a high molecule, 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, 100000 or more, 300000 or more, or 500000 or more, and may also be 10000000 or less, 7500000 or less, 5000000 or less, 3000000 or less, 1000000 or less, 750000 or less, 500000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 10000 or less, 7500 or less, 5000 or less, or 3000 or less.

[0025] The melting point of the wax may be 30°C or more, 40°C or more, 50°C or more, 60°C or more, 80°C or more, 100°C or more, or 120°C or more, preferably 40°C or more, particularly preferably 55°C or more, and may also be 250°C or less, 225°C or less, 200°C or less, 150°C or less, 130°C or less, 120°C or less, 110°C or less, 100°C or less, 80°C or less, or 50°C or less, preferably 120°C or less. The melting point of the wax may be measured in accordance with JIS K 2235-1991. The melting point generally corresponds to the peak top temperature of the endothermic peak at the maximum temperature before melting observed in DSC (differential scanning calorimetry).

[0026] of the wax 1The 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 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 also be 25 or less, 22 or less, 20 or less, 18 or less, 16 or less, 14 or less, or 12 or less. In one aspect, it is 9 or more and 20 or less, for example, 9.5 or more and 14 or less. When the integral value ratio is high, for example, not less than the above lower limit value, in the case of wax, the abundance ratio of methylene hydrogen can be higher than that of methyl hydrogen and the hydrocarbon may have a less branched structure. With such a structure, it is presumed that the effects of the present disclosure can be achieved well. 1 The 1H-NMR measurement is performed on a solution sample obtained by dissolving wax in deuterated chloroform.

[0027] In the temperature variable X-ray diffraction measurement of 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 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 also be 1.2 or less, 1.0 or less, 0.9 or less, 0.8 or less, or 0.7 or less. In one aspect, it is 0.3 or more and 1.0 or less, for example, 0.5 or more and 0.9 or less. When the diffraction intensity ratio is high, for example, not less than the above lower limit value, in the case of wax, it has a specific crystal structure even at 60°C. With such a structure, it is presumed that the effects of the present disclosure can be achieved well. The temperature variable X-ray diffraction measurement is performed by using Cu Kα ray as the light source, cooling to -20°C under a nitrogen atmosphere, then heating to 25°C or 60°C at 5°C / min, holding for 5 minutes, and then measuring. As the measuring apparatus, SmartLab of RIGAKU can be used.

[0028] [Type 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; synthetic waxes such as Fischer-Tropsch wax, polyethylene wax, and polypropylene wax. Preferably, it is 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 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 in the repellent, and may also 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 in the present disclosure may contain a dispersant. The dispersant may be at least one selected from organic dispersants and inorganic dispersants. The dispersant may be at least one selected from anionic dispersants, nonionic dispersants, cationic dispersants, amphoteric dispersants, and inorganic dispersants.

[0031] Each of the organic dispersant and the inorganic dispersant may be used as the dispersant, or a combination of the organic dispersant and the inorganic dispersant may be used.

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

[0033] The dispersant may be non-fluorine.

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

[0035] The nonionic dispersant may be of low molecular weight (for example, a molecular weight of 2000 or less, particularly 10000 or less), or may be of high molecular weight (for example, a molecular weight of 2000 or more). The molecular weight of the nonionic dispersant may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 1000000 or less, 750000 or less, 500000 or less, 250000 or less, 100000 or less, 50000 or less, 10000 or less, 7500 or less, 5000 or less, 25000 or less, 750 or less, or 250 or less.

[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 an ester is an ester of an alcohol and a fatty acid. Examples of alcohols are alcohols having 1 to 30 valences (particularly 2 to 10 valences) and 1 to 50 carbon atoms (particularly 10 to 30 carbon atoms) (for example, aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0039] Examples of ester ethers are compounds in which an alkylene oxide (especially ethylene oxide) is added to an ester of an alcohol and a fatty acid. Examples of alcohols are alcohols having 1 to 30 valences (especially 2 to 10 valences) and 1 to 50 carbon atoms (especially 3 to 30 carbon atoms) (for example, aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

[0040] Examples of alkanolamides are formed from fatty acids and alkanolamines. The alkanolamide may be a monoalkanolamide or a dialkanolamine. Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms. The alkanolamine may be an alkanol having 1 to 3 amino groups and 1 to 5 hydroxyl groups and 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

[0041] The polyol may be an alcohol having 2 to 5 valences and 10 to 30 carbon atoms. The amine oxide may be an oxide of an amine (secondary amine or preferably tertiary amine) (for example having 5 to 50 carbon atoms).

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

[0043] The nonionic dispersant is selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyols and amine oxides, and preferably is a nonionic dispersant having an oxyalkylene group.

[0044] Nonionic dispersants may include alkylene oxide adducts of linear and / or branched aliphatic (saturated and / or unsaturated) groups, polyalkylene glycol esters of linear and / or branched fatty acids (saturated and / or unsaturated), sorbitan esters of linear and / or branched fatty acids (saturated and / or unsaturated), glycerin esters of linear and / or branched fatty acids (saturated and / or unsaturated), polyglycerin esters of linear and / or branched fatty acids (saturated and / or unsaturated), sucrose esters of linear and / or branched fatty acids (saturated and / or unsaturated), polyoxyethylene (POE) / polyoxypropylene (POP) copolymers (random copolymers or block copolymers), alkylene oxide adducts of acetylene glycols, and the like. Among these, those in which the structure of the alkylene oxide adduct portion and the polyalkylene glycol portion is polyoxyethylene (POE) or polyoxypropylene (POP) or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred. Also, the nonionic dispersant may not contain an aromatic group.

[0045] The nonionic dispersant has the formula: R 1 O-(CH2CH2O) p -(R 2 O) q -R 3 [wherein R 1 is an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or an acyl group, each of R 2 is independently the same or different and is an alkylene group having 3 or more carbon atoms (for example, 3 to 10), R 3 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms, p is a number of 2 or more, q is 0 or a number of 1 or more.] It may be a compound represented by

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

[0047] Specific examples of the nonionic dispersant include condensation products of ethylene oxide with hexylphenol, isooctylphenol, hexadecanol, oleic acid, alkane (C 12 -C 16 ) thiol, sorbitan monofatty acid (C7-C 19 ) or alkyl (C 12 -C 18 ) amine, etc., sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, lecithin derivatives, etc. Examples of the nonionic dispersant include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylenepolyoxybutylene alkyl ethers, polyoxyethylene polyoxypropylene glycols, polyethyleneimine ethoxylates, etc.

[0048] The proportion of the polyoxyethylene block can be 5 to 80% by weight, for example 30 to 75% by weight, particularly 40 to 70% by weight, based on the molecular weight of the nonionic dispersant (copolymer). The average molecular weight of the nonionic dispersant is generally 300 to 5,000, for example, 500 to 3,000. The nonionic dispersant may be a single type or a mixture of two or more types. The nonionic dispersant may be a mixture of a compound having an HLB (hydrophilic-lipophilic balance) of less than 15 (particularly 5 or less) and a compound having an HLB of 15 or more. Specifically, it is preferably selected from polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene, polyoxypropylene having an HLB of 1 to 18, and sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters having an HLB value of less than 7.

[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 of a low molecular weight type (for example, having a molecular weight of 2,000 or less, particularly 10,000 or less) or a high molecular weight type (for example, having a molecular weight of 2,000 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 also 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, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 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 ethylene oxide-added type ammonium salt. Specifically, amine salt type dispersants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, etc.; quaternary ammonium salt type dispersants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzalkonium chloride, benzethonium chloride, etc.; polymeric cationic dispersants such as polyquaternium-1 to 47, etc. Examples of the cationic dispersant include alkylamine salts, quaternary ammonium salts, etc.

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

[0053] Specifically, the low-molecular-weight cationic dispersant has the formula: R 1 p -N +R 2 q X - [In the formula, R 1 is a linear and / or branched aliphatic (saturated and / or unsaturated) group having 12 or more carbon atoms (for example, C 12 ~C 50 ), and R 2 is H or an alkyl group having 1 to 4 carbon atoms, a benzyl group, a polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (especially 2, particularly 3) to 50) (CH3 and C2H5 are particularly preferred), X is a halogen atom (for example, chlorine), or a fatty acid salt having 1 to C4, or a sulfonate having 1 to C4, p is 1 or 2, q is 2 or 3, and p + q = 4.] It may be an ammonium salt represented by. The carbon number of R 1 may be 12 to 50, for example, 12 to 30.

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

[0055] The polymeric cationic dispersant may be various polymers having cationic groups (e.g., ammonium group, quaternary ammonium group) (e.g., polyquaternium-1 to 47). Examples of the polymeric cationic dispersant include cationized starches, cationized celluloses (e.g., O-(2-hydroxy-3-(trimethylammonio)propyl) hydroxyethyl cellulose chloride), cationized guar gums, cationized xanthan gums, cationized natural products such as chitosan (especially cationized saccharides); polymers of cationic group-containing monomers such as aziridine, vinylimidazole, aminoalkyl methacrylate, N,N,N',N'-tetramethyl-2-butene-1,4-diamine, quaternized dimethylammonium ethyl methacrylate, diallyldimethylammonium chloride, dimethylaminopropylamine, quaternized vinylimidazole, and the like.

[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 of low molecular weight (e.g., molecular weight 2000 or less, especially 10000 or less) or of high molecular weight (e.g., molecular weight 2000 or more). The molecular weight of the anionic dispersant may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 1000000 or less, 750000 or less, 500000 or less, 250000 or less, 100000 or less, 50000 or less, 10000 or less, 7500 or less, 5000 or less, 25000 or less, 750 or less, or 250 or less.

[0058] Examples of anionic dispersants include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfonated fatty acid salts, N-acyl amino acid type dispersants, phosphoric acid mono- or diester type dispersants, and sulfosuccinic acid esters. As an example of an anionic dispersant, carboxylate salts (e.g., fatty acid salts) etc. can be mentioned.

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

[0060] The amphoteric dispersant may be of low molecular weight type (e.g., molecular weight 2000 or less, especially 10000 or less), or may be of high molecular weight type (e.g., molecular weight 2000 or more). The molecular weight of the amphoteric dispersant may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 1000000 or less, 750000 or less, 500000 or less, 250000 or less, 100000 or less, 50000 or less, 10000 or less, 7500 or less, 5000 or less, 25000 or less, 750 or less, or 250 or less.

[0061] Examples of amphoteric dispersants include alanines, imidazolinium betaines, amide betaines, betaine acetate, etc., and specifically, lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylamino acetate betaine, fatty acid amide propyl dimethylamino acetate betaine, etc. can be mentioned.

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

[0063] The average primary particle diameter of the inorganic dispersant may be 5 nm or more, 30 nm or more, 100 nm or more, 1 μm or more, 10 μm or more, or 25 μm or more, and may also be 100 μm or less, 50 μm or less, 10 μm or less, 1 μm or less, 500 nm or less, or 300 nm or less. The average primary particle diameter 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 the inorganic dispersant 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 the dispersant may be 0.01 part by weight or more, 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, based on 100 parts by weight of the wax, and may also be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less.

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

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

[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, or 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, per 1 part by weight of the wax, and may also be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less.

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

[0070] The amount of the organic solvent may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more with respect to 1 part by weight of the wax, and may also be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less.

[0071] 〔Silicone〕 The water repellent agent in the present disclosure may contain silicone (polyorganosiloxane). By containing silicone, in addition to good water repellency, it can also have good texture and durability.

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

[0073] The weight average molecular weight of the silicone may be 1000 or more, 10000 or more, or 50000 or more, and may also be 500000 or less, 2500000 or less, 100000 or less, or 50000 or less.

[0074] [Amount of silicone] The amount of silicone may be 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, based on 100 parts by weight of the wax, and may also be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

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

[0076] [Amount of organic acid] The amount of organic acid may be 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, based on 100 parts by weight of the wax, and may also be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less. The amount of the organic acid may be adjusted so that the pH of the water repellent is 3 - 10, for example 5 - 9, particularly 6 - 8. The water repellent may be acidic (pH 7 or less, for example 6 or less).

[0077] [Inorganic acid] The sizing agent 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, etc. In the present disclosure, one kind of inorganic acid may be used, or two or more kinds may be used in combination. By adding an inorganic acid, the stability of the aqueous dispersion can be improved.

[0078] [Amount of inorganic acid] The amount of inorganic acid may be 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, based on 100 parts by weight of the wax. Also, it may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less. The amount of inorganic acid may be adjusted so that the pH of the sizing agent is 3 - 10, for example 5 - 9, particularly 6 - 8. The sizing agent may be acidic (pH 7 or less, for example 6 or less).

[0079] [Hardening agent] The sizing agent of the present disclosure may contain a hardening agent (active hydrogen - reactive compound or active hydrogen - containing compound). When the sizing agent is for paper (for example, an oil - resistant agent for paper), it may not contain a hardening agent.

[0080] [Other components] The water and / or oil repellent may contain other components in addition to the above components. Examples of other components include polysaccharides, flocculants, yield improvers, coagulants, binder resins, anti-slip agents, sizing agents, paper strength enhancers, fillers, antistatic agents, preservatives, ultraviolet absorbers, antibacterial agents, deodorants, fragrances, and the like. These may be used alone or in combination of two or more. In addition to the above components, as other components, other water and / or oil repellents, dispersants, hand modifiers, softeners, flame retardants, paint fixatives, anti-wrinkle agents, drying rate adjusters, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity adjusters, ultraviolet absorbers, antioxidants, pH adjusters, insect repellents, defoamers, shrinkage preventers, anti-wrinkle agents for washing, shape retainers, drape retainers, ironing property improvers, brighteners, whitening agents, fabric softening clay, migration inhibitors such as polyvinylpyrrolidone, polymer dispersants, soil release agents, scum dispersants, fluorescent brighteners such as 4,4-bis(2-sulfostyryl)biphenyl disodium (Tinopearl CBS-X manufactured by Ciba Specialty Chemicals), dye fixatives, anti-fading agents such as 1,4-bis(3-aminopropyl)piperazine, stain removers, enzymes such as cellulase, amylase, protease, lipase, keratinase, etc. as fiber surface modifiers, defoaming agents, silk protein powder, surface modified products thereof or emulsion dispersions (for example, K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical Co., Ltd.), hydrolyzed silk solution (Jomo), Silkgen G Soluble S (Ichimaru Pharcos)) that can impart silk-like texture and functions such as moisture absorption and release, anti-pollution agents (for example, nonionic polymer compounds composed of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units (for example, FR627 manufactured by Gohou Chemical Industry Co., Ltd.), SRC-1 manufactured by Clariant Japan, etc.) can be blended. These may be used alone or in combination of two or more. The components may be appropriately determined according to the use of the water and / or oil repellent.

[0081] [Amount of other components] The amount of each or the total amount of other components may be 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, based on 100 parts by weight of the wax, and may also be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0082] <Pulp composition> The pulp composition in the present disclosure contains wax and a pulp base material. The pulp composition in the present disclosure can be excellent in oil resistance.

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

[0084] The pulp composition in the present disclosure may not have any selected from the group consisting of a compound having a fluoroalkyl group with 8 or more carbon atoms, a compound having a perfluoroalkyl group with 8 or more carbon atoms, a compound having a fluoroalkyl group with 4 or more carbon atoms, a compound having a perfluoroalkyl group with 4 or more carbon atoms, a compound having a perfluoroalkyl group, a compound having a fluoroalkyl group, and a compound having a fluorine atom. The pulp composition in the present disclosure can impart water-repellency to the base material 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 amounts of the respective components may be adjusted so as to obtain such a pH.

[0086] 〔Pulp base material〕 The pulp composition contains a pulp base material. The pulp base material is composed of pulp, and the pulp may be wood pulp, non-wood pulp, waste paper pulp, etc.

[0087] [Wood pulp] Examples of wood pulp include softwood kraft pulp obtained from conifers such as the genus Pinus and the genus Abies, and hardwood kraft pulp obtained from genera such as Acacia, Eucalyptus, Fagus, and Populus (e.g., Poplar). Examples of softwood kraft pulp include, for example, unbleached softwood kraft pulp (NUKP), bleached softwood pulp (NBKP), semi-bleached softwood kraft pulp (NSBKP), softwood sulfite pulp, etc. Also, examples of hardwood kraft pulp include, for example, unbleached hardwood kraft pulp (LUKP), bleached hardwood kraft pulp (LBKP), semi-bleached hardwood kraft pulp (LSBKP), hardwood sulfite pulp, etc. Note that the pulp used can be used alone or in combination. In addition to kraft pulp, in addition to softwood kraft pulp and hardwood kraft pulp, there are also mechanical pulps such as stone ground pulp (SGP), pressurized groundwood pulp (PGW), refiner ground pulp (RGP), thermomechanical pulp (TGP), chemiground pulp (CGP), groundwood pulp (GP), and thermomechanical pulp (TMP). Furthermore, examples of waste paper pulp include deinked waste paper pulp, deinked and de-inked waste paper pulp, or deinked, de-inked, and bleached waste paper pulp produced from tea waste paper, kraft envelope waste paper, magazine waste paper, newspaper waste paper, flyer waste paper, office waste paper, cardboard waste paper, high-quality waste paper, Kent waste paper, imitation waste paper, deed waste paper, etc.

[0088] [Non-wood pulp] Examples of non-wood pulp include pulp obtained from bagasse, kenaf, bamboo, linters, cotton, linen, hemp, ramie, straw, esparto, manila hemp, sisal hemp, jute, flax, ganpi, mitsumata, kozo, etc.

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

[0090] [Fiber width of pulp] The average fiber diameter of the pulp is preferably 5 μm or more, more preferably 10 μm or more, still more preferably 15 μm or more, from the viewpoint of improving oil resistance, and preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less.

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

[0092] [Amount of pulp substrate] The amount of the pulp substrate 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, or 90 wt% or more in the pulp composition, and may also 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. When the pulp composition is prepared by internal addition, the amount of the pulp substrate may be 30 wt% or less in the pulp composition, and when the pulp composition is prepared by external addition, the amount of the pulp substrate may be 75 wt% or more in the pulp composition.

[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 also be 99.9% by weight or less, 95% by weight or less, 90% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, or 55% by weight or less.

[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 sizing agent.

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

[0096] [Wax] The pulp composition contains wax, particularly hydrocarbon wax. For details of the types of wax, the description of wax in <Sizing agent> is incorporated by reference.

[0097] [Amount of wax] The amount of wax may be 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more based on the pulp base material, preferably 0.5% by weight or more. Also, it 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 externally added to the surface of the pulp base material (such as pulp products like paper, paper containers, and pulp molded products). The amount of wax contained in the coating layer formed by the external addition treatment is 0.01 g / m 2 or more, 0.03 g / m 2 or more, 0.05 g / m 2 or more, 0.1 g / m 2 or more, 0.3 g / m 2 or more, 0.5 g / m 2 or more, or 1.0 g / m 2 or more, and may also be 5.0 g / m 2 or less, 4.0 g / m 2 or less, 3.0 g / m 2 or less, 2.0 g / m 2 or less, 1.0 g / m 2 or less, 0.5 g / m 2 or less, 0.3 g / m 2 or less, or 0.1 g / m 2 or less.

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

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

[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, thermo-chemically modified starch, oxidized starch, esterified starch, etherified starch (for example, hydroxyethylated starch, etc.), aldehyde-modified starch, cationized starch, starch, xanthan gum, karaya gum, welan gum, guar gum, pectin, tamarind gum, carrageenan, chitosan, gum arabic, locust bean gum, cellulose, alginic acid, agar, dextran, cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, chitin nanofibers, cellulose nanofibers, and pullulan, and modified polysaccharides thereof (for example, modified polysaccharides into which hydroxyl groups or cationic groups are introduced); Polyamide-based paper strength agents such as polyamide resin, polyamine resin, polyamide-polyamine resin, polyamide-epichlorohydrin resin, polyamide-polyamine-epichlorohydrin resin, polyamide-polyurea-formaldehyde resin, and epoxidized polyamide resin; Urea / melamine-based paper strength agents such as urea resin, melamine resin, urea-formaldehyde resin, and melamine-formaldehyde resin; Polyvinyl alcohol-based paper strengthening agents such as polyvinyl alcohol, fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, cation-modified polyvinyl alcohol, and terminal alkyl-modified polyvinyl alcohol; Examples include styrene-butadiene copolymers, polyvinyl acetate, vinyl chloride-vinyl acetate copolymers, polyvinyl chloride, polyvinylidene chloride, polyacrylate esters, fatty acid diamides, polyethyleneimine resins, and ketone aldehyde resins. As the paper strengthening agent in the present disclosure, a polyacrylamide-based paper strengthening agent, a polysaccharide-based paper strengthening agent, or a polyamide-based paper strengthening agent is preferable.

[0102] [Amount of paper strengthening agent] The amount of the paper strengthening agent may be 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more with respect to the pulp, and may also be 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, preferably 5.0% by weight or less.

[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. Examples include rosin-based sizing agents (e.g., acidic rosin-based sizing agents, neutral rosin-based sizing agents), alkyl ketene dimers, alkenyl succinic anhydrides, etc.

[0104] [Amount of sizing agent] The amount of the sizing agent may be 0.1% by weight or more, 0.2% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more with respect to the pulp, and may also be 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less.

[0105] 〔Other additives〕 In addition to the above, the pulp composition may also contain other additives such as known paper-use combined chemicals used in the production of pulp products, such as fixing agents (such as aluminum sulfate), coagulants / flocculants (such as polyamine resins), yield improvers (such as polyacrylamide resins), organic acids (such as formic acid and acetic acid), dyes, slime control agents, and defoaming agents.

[0106] [Amount of other additives] The amount of each of the other additives may be 0.01% by weight or more, 0.1% by weight or more, 1% by weight or more, 3% by weight or more, or 5% by weight or more with respect to the pulp substrate, and may also be 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, 3% by weight or less, or 1% by weight or less.

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

[0108] The substrate to be treated with the treating agent in the present disclosure is not limited, but is preferably a fiber substrate (fiber base material), particularly may be a textile substrate (fabric base material) or a pulp substrate (paper base material), and particularly a pulp substrate.

[0109] Examples of the fiber substrate include animal and plant natural fibers such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semi-synthetic fibers such as rayon and acetate, inorganic fibers such as glass fiber, carbon fiber, and asbestos fiber, or a mixed fiber thereof. The fiber products include woven fabrics, knitted fabrics, and non-woven fabrics, fabrics in the form of clothing (e.g., water-repellent clothing, e.g., raincoats), and carpets. However, the fibers, yarns, and intermediate fiber products (e.g., sliver or roving, etc.) in the state before being made into a fabric may be treated.

[0110] The substrates to be treated with the treatment agent of the present disclosure are not limited to fiber substrates, and others include stone, filters (e.g., electrostatic filters), dust masks, parts of fuel cells (e.g., gas diffusion electrodes and gas diffusion supports), glass, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plasters, etc.

[0111] When the base material is glass, the manufactured glass product may be an optical member. Some layer (or film), such as a hard coat layer or an antireflection layer, may be formed on the surface (outermost layer) of the glass base material. Either a single-layer antireflection layer or a multilayer antireflection layer may be used for the antireflection layer. Examples of inorganic substances that can be used for the antireflection layer include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, CeO2, MgO, Y2O3, SnO2, MgF2, WO3, etc. These inorganic substances may be used alone or in combination of two or more of them (for example, as a mixture). When forming a multilayer antireflection layer, it is preferable to use SiO2 and / or SiO for its outermost layer. When the article to be manufactured is an optical glass component for a touch panel, it may have a thin film using a transparent electrode, such as indium tin oxide (ITO) or indium zinc oxide, on a part of the surface of the base material (glass). Further, depending on its specific specifications, etc., the base material may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), a matte film layer, a hard coating film layer, a polarizing film, a retardation film, and a liquid crystal display module, etc.

[0112] 〔Manufacturing method of pulp product〕 The pulp product (paper product) in the present disclosure can be obtained by subjecting a pulp composition obtained by treating a pulp base material with a water repellent containing wax to treatment steps such as drying, heating, and molding, if necessary.

[0113] The sizing agent in the present disclosure can be applied to a pulp substrate by a conventionally known method as a treating agent (especially a surface treating agent). As a treatment method, the sizing agent in the present disclosure can be dispersed and diluted in an organic solvent or water if necessary, and then adhered to the inside and / or surface of the pulp substrate by a known method such as dip coating, spray coating, foam coating, etc., and then dried. The dilution ratio may be appropriately changed depending on the concentration and use of the sizing agent, but may be 3 to 2000 times, for example, 10 to 100 times. After drying, a pulp product with the solid component of the sizing agent adhered thereto is obtained. Further, if necessary, it may be applied together with a suitable crosslinking agent and cured.

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

[0115] As a method for treating a pulp base material, an internal addition treatment method of adding a sizing agent to the pulp base material before papermaking (for example, in the form of a pulp slurry), or an external addition treatment method of applying a sizing agent to the pulp base material after papermaking (for example, a pulp product) can be used. Examples of the internal addition treatment method include mixing, dipping, etc., and may include a step of adding a sizing agent to the pulp slurry and stirring and mixing. Examples of the external addition treatment method include spraying, coating, dipping treatment, foam coating, etc., and specifically, a pond type two-roll size press, a gate roll type, and a rod metering size press, etc. can be mentioned. The treatment may be an external addition treatment or an internal addition treatment. For example, when the pulp base material is paper, it may be coated on the paper, or a solution may be adhered or sprayed on the paper, or it may be mixed and treated with the pulp slurry before papermaking. When the pulp base material is a fiber material, examples of the treatment method include padding treatment, dipping treatment, spraying treatment, and coating treatment. As the padding treatment, for example, a method using a padding device described on pages 396-397 of the Fiber Dyeing Processing Dictionary (published in 1963 by Nikkan Kogyo Shimbun Co., Ltd.) or pages 256-260 of Color Dyeing Chemistry III (published in 1975 by Jitskyo Publishing Co., Ltd.) can be mentioned. As the coating treatment, for example, a method using a coating machine described on pages 473-477 of the General List of Dyeing Finishing Equipment (published in 1981 by Sen'i Shuppan Co., Ltd.) can be mentioned. As the dipping treatment, for example, a method using a batch type dyeing machine described on pages 196-247 of the General List of Dyeing Finishing Equipment (published in 1981 by Sen'i Shuppan Co., Ltd.) can be mentioned, and a liquid flow dyeing machine, an air flow dyeing machine, a drum dyeing machine, a winch dyeing machine, a washer dyeing machine, a cheese dyeing machine, etc. can be used. As the spraying treatment, for example, an air spray that atomizes the treatment liquid with compressed air and sprays it, or a method using an air spray of a hydraulic atomization method can be mentioned.

[0116] The treatment method may be an internal addition treatment in which a sizing agent is added to the pulp slurry before papermaking. The internal addition treatment may include one or more of the steps of adding a sizing agent to the pulp slurry and stirring and mixing it, sucking and dehydrating the pulp composition prepared in this step through a reticular body of a predetermined shape to deposit the pulp composition to form an intermediate of a pulp molded product, and forming and drying the intermediate of the pulp molded product with a heated mold to obtain a pulp molded product, but it is not limited to this. The treated paper may be optionally heat-treated depending on the properties of the paper after simple drying at room temperature or high temperature. The temperature of the heat treatment may be 150 °C or higher, 180 °C or higher, or 210 °C or higher, may be 300 °C or lower, 250 °C or lower, or 200 °C or lower, and particularly may be 80 °C to 180 °C. By performing the heat treatment within such a temperature range, excellent oil resistance and the like can be exhibited. An external addition treatment may be performed on the internally added pulp base material, treated with a sizing agent, and further wax or sizing agent may be adhered to the surface.

[0117] The treatment method may be an external addition treatment in which a sizing agent is applied to the pulp base material after papermaking. The size press of the external addition treatment can also be classified as follows by the coating method. One coating method is a so-called pond type two-roll size press in which a coating liquid (size liquid) is supplied to a nip portion formed by passing paper between two rubber rolls to create a coating liquid reservoir called a pond, and the size liquid is applied to both sides of the paper by passing the paper through this coating liquid reservoir. Another coating method is a gate roll type in which the size liquid is applied by a surface transfer type, and a rod metering size press. In the pond type two-roll size press, the size liquid easily penetrates into the paper, and in the surface transfer type, the size liquid components tend to remain on the surface of the paper. The surface transfer type has a coating layer that tends to remain on the surface of the paper compared to the pond type two-roll size press, and the coating layer formed on the surface is more than that of the pond type two-roll size press. In the present disclosure, the performance can be imparted to the paper even when the former pond type two-roll size press is used. The paper treated in this way may be optionally heat-treated up to 300 °C, for example up to 200 °C, particularly in the temperature range of 80 °C to 180 °C depending on the properties of the paper after simple drying at room temperature or high temperature, and can exhibit excellent oil resistance and the like.

[0118] Specific examples of pulp products include paper, paper containers, pulp molded products, food packaging materials, food containers, base paper for gypsum board, base paper for coating, medium-quality paper, general liners and cores, neutral pure white roll paper, neutral liners, rust-proof liners and metal laminated paper, kraft paper, neutral printing and writing paper, neutral base paper for coating, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper, and the like. Examples of preferred pulp products include food packaging materials and food containers, for example, 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.

Examples

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

[0121] The test procedure is as follows.

[0122] [Volume occupancy ratio of particles of 10 μm or more] From the volume-based frequency distribution (volume distribution) obtained by measurement with a laser diffraction / scattering device of the water-dispersible oil-resistant agent, the occupancy ratio of particles of 10 μm or more was calculated, and the value was taken as the volume occupancy ratio of particles of 〉10 μm.

[0123] [Volume occupancy ratio of particles of 100 μm or more] From the volume-based frequency distribution (volume distribution) obtained by measurement with a laser diffraction / scattering device of the water-dispersible oil-resistant agent, the occupancy ratio of particles of 100 μm or more was calculated, and the value was taken as the volume occupancy ratio of particles of 〉100 μm.

[0124] [Median diameter D50] It was determined by measurement with a laser diffraction / scattering device of the water-dispersible oil-resistant agent.

[0125] [Ionic charge density] The ionic charge density in the oil-resistant agent of the present disclosure can be measured, for example, by the following method. Using a sample solution with a solid content of 0.1 g / L, measure the anion demand with a particle charge meter (MUTEK PCD-04 manufactured by BTG) using a 1 / 1000 normal potassium polyvinyl sulfonate solution, and calculate the ionic charge density (cation charge density) from the following formula (1). Alternatively, measure the cation demand in the same manner using a diallyldimethylammonium chloride solution instead of potassium polyvinyl sulfonate, and calculate the ionic charge density (anion charge density) from the following formula (1). Ionic charge density (μeq / g) = A / B (1) A: Cation demand or anion demand (μeq / L) B: Sample solution concentration (g / L)

[0126] [Preparation of pulp mold] Using an automatic mold forming machine, a pulp mold was formed. A reticulated body was placed on a metal pulp mold forming die provided with a large number of suction holes at the bottom, and a metal tank was placed at the top. A mixture of pulp slurry and a water-dispersible oil-resistant agent was placed in the upper metal tank. From the side opposite to the side where the reticulated body of the pulp mold forming die was placed, the pulp-containing aqueous composition was suctioned and dehydrated through the pulp mold forming die and the reticulated body by a vacuum pump, and the solid content (pulp, etc.) contained in the pulp-containing aqueous composition was deposited on the reticulated body to obtain a pulp mold intermediate. Next, the obtained pulp mold intermediate was dried under a pressure of 0.05 to 5 MPa from above and below with a metal osmosis forming die heated to 60 to 250 °C. Thereby, a pulp mold product formed in the shape of a container was manufactured.

[0127] [Practical oil resistance test at 65 °C] Pretreatment was performed by storing the pulp mold under the conditions of 23 °C and 50% humidity for 12 hours. 100 ml of corn oil at 65 °C was poured into the pulp mold, left at room temperature for 45 minutes, then the corn oil was taken out from the pulp mold, and the degree of oil stain on the pulp mold was evaluated. Evaluation values were set as follows according to the degree of penetration. 5: No penetration inside 4: Penetration inside. No penetration on the back side. 3: Penetration inside. Slight bleeding on the back side. 2: Penetration inside. Bleeding to the back side is less than 50% of the area. 1: Penetration inside. Bleeding to the back side is 50% or more and less than 100% of the area. 0: Bleeding throughout the back side.

[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). The DSC measurement was performed under a nitrogen atmosphere. After cooling to -20°C, the endothermic peak observed during the heating process to 180°C at a rate of 10°C / min was measured. When multiple endothermic peaks appeared, the endothermic peak on the highest temperature side was taken as the maximum endothermic peak, and the peak top was taken as the maximum endothermic peak temperature. The maximum endothermic peak temperature corresponds to the melting point of the wax. The endothermic heat quantity was calculated by calculating the heat quantity in the range of ±10°C of the endothermic peak temperature.

[0129] [Temperature-Variable X-ray Diffraction Measurement of Wax] The crystalline state of the wax was measured by X-ray diffraction method (XRD) using RIGAKU's SmartLab. Cu Kα ray was used as the light source. The temperature-variable XRD (XRD-DSC) measurement was performed under a nitrogen atmosphere. After cooling to -20°C, the temperature was raised to 25°C or 60°C at a rate of 5°C / min, held for 5 minutes, and then the measurement was carried out. The full width at half maximum of the peak was defined as the width of 2θ 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 region of 2θ from 15° to 30° at the measurement temperature of 25°C was taken as [peak intensity A25°C]. Also, the intensity of the maximum point of the diffraction intensity in the region of 2θ from 15° to 30° at the 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] as follows. Folding strength ratio [A60°C / A25°C] = [Peak strength A60°C] / [Peak strength A25°C]

[0130] [For wax 1 1H-NMR spectrum measurement] For wax 1 The 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 of wax 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) 1 the 1H-NMR spectrum was measured. The reference of the chemical shift was set so that the peak of tetramethylsilane (TMS) was at 0 ppm in the obtained spectrum. The phase was adjusted by performing first-order phase correction in the region of the chemical shift of TMS and second-order phase correction in the region of the chemical shift of deuterated chloroform to adjust the flatness of the signal. The integral value of the signal in the range of chemical shift from 0.79 ppm to 0.93 ppm was calculated, and the integral value was set to 6 and taken as [Integral value A]. Then, the integral value of the signal observed in the range of chemical shift from 1.05 ppm to 1.47 ppm or less was calculated and taken 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 removal of the liquid medium from the oil-resistant agent was performed by naturally drying the liquid medium at room temperature and then drying it under reduced pressure for 24 hours. DSC measurements were carried out by cooling to -20°C under a nitrogen atmosphere and then measuring the endothermic peak observed during the heating process to 180°C at a rate of 10°C / min. When multiple endothermic peaks appeared, the endothermic peak on the highest temperature side was taken as the maximum endothermic peak, and the peak top was taken as the maximum endothermic peak temperature. The endothermic heat quantity was calculated by calculating the heat quantity in the range of ±10°C of the endothermic peak temperature.

[0132] [Measurement of the temperature-variable X-ray diffraction method of the solid component obtained by removing the liquid medium from the oil-resistant agent] The crystal state of the solid component obtained by removing the liquid medium from the oil-resistant agent was measured by X-ray diffraction method (XRD) using RIGAKU's SmartLab. Cu Kα rays were used as the light source. Temperature-variable XRD (XRD-DSC) measurements were carried out under a nitrogen atmosphere. After cooling to -20°C, the temperature was raised to 25°C or 55°C at a rate of 5°C / min, held for 5 minutes, and then the measurement was performed. The half-width of the peak was defined as the width of 2θ 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 point of the diffraction intensity in the region of 2θ from 15° to 30° at the measurement temperature of 25°C was taken as [peak intensity A25°C]. Also, the intensity of the maximum point of the diffraction intensity in the region of 2θ from 15° to 30° at the 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] as follows. Diffraction intensity ratio [A60°C / A25°C] = [peak intensity A60°C] / [peak intensity A25°C] The removal of the liquid medium from the oil-resistant agent was carried out by natural drying at room temperature and then drying under reduced pressure for 24 hours.

[0133] [Evaluation Example 1] As waxes, 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.) were used to perform differential scanning calorimetry, temperature-variable X-ray diffraction measurement, and 1 H-NMR spectrum measurement. The maximum endothermic peak temperature in differential scanning calorimetry and the [peak intensity A25°C] at the measurement temperature of 25°C and the [peak intensity A60°C] at the measurement temperature of 60°C in temperature variable X-ray diffraction measurement, and the diffraction intensity ratio [A60°C / A25°C] calculated therefrom, 1 The results of 1H-NMR spectrum measurement are shown in Table 1.

[0134] [Example 1] 2 g of HNP-3 (manufactured by Nippon Seiro Co., Ltd.) as wax, 0.2 g of polyethylene oxide alkyl ether (alkyl carbon number 6-16, HLB: 7), and 17.8 g of water were mixed to obtain an aqueous dispersion. After heating this aqueous dispersion to 85°C, it was treated with an ultrasonic homogenizer for 20 minutes to obtain an oil-resistant agent in aqueous dispersion form. The obtained oil-resistant agent in aqueous dispersion form showed the following characteristics. Median diameter D50: 0.9 μm Volume ratio of particles of 100 μm or more: 0% Volume ratio of particles of 10 μm or more: 9% Charge density: 21 μeq / g The oil-resistant agent in aqueous dispersion form was added to an aqueous pulp slurry with a concentration of 0.5 wt% so that the ratio to the pulp was 5 wt% in terms of solid content, and a pulp composition was prepared. The pulp-containing oil-resistant agent in aqueous dispersion form was put into an automatic mold forming machine to produce a pulp mold. When the pulp mold was subjected to a practical oil resistance test at 65°C, it was 4 points. In addition, the results of temperature variable X-ray diffraction measurement of the solid component obtained by removing the liquid medium from the oil-resistant agent in aqueous dispersion form are shown in Table 2.

[0135] [Example 2] 2 g of HNP-10 (manufactured by Nippon Seiro Co., Ltd.) as wax, 0.2 g of polyethylene oxide alkyl ether (alkyl carbon number 6-16, HLB: 7), and 17.8 g of water were mixed to obtain an aqueous dispersion. After heating this aqueous dispersion to 85°C, it was treated with an ultrasonic homogenizer for 20 minutes to obtain an oil-resistant agent in aqueous dispersion form. The obtained oil-resistant agent in aqueous dispersion form showed the following characteristics. Median diameter D50: 0.9 μm Volume percentage of particles of 100 μm or more: 0% Volume percentage of particles of 10 μm or more: 11% Charge density: 19 μeq / g A water-dispersible oil-resistant agent was added to an aqueous pulp slurry with a concentration of 0.5 wt% so that the ratio in terms of solid content was 5 wt% with respect to the pulp, and a pulp composition was prepared. The pulp-containing water-dispersible oil-resistant agent was put into an automatic mold forming machine to produce a pulp mold. When the pulp mold was subjected to a practical oil resistance test at 65°C, the result was 4 points. Table 2 shows the results of temperature variable X-ray diffraction measurement of the solid component obtained by removing the liquid medium from the water-dispersible oil-resistant agent.

[0136] [Example 3] 2 g of HNP-51 (manufactured by Nippon Seiro Co., Ltd.) as wax, 0.2 g of polyethylene oxide alkyl ether (alkyl carbon number 6 - 16, HLB: 7), and 17.8 g of water were mixed to obtain a water dispersion. After heating this water dispersion to 85°C, it was treated with an ultrasonic homogenizer for 20 minutes to obtain a water-dispersible oil-resistant agent. The obtained water-dispersible oil-resistant agent showed the following characteristics. Median diameter D50: 0.8 μm Volume percentage of particles of 100 μm or more: 0% Volume percentage of particles of 10 μm or more: 12% Charge density: 25 μeq / g A water-dispersible oil-resistant agent was added to an aqueous pulp slurry with a concentration of 0.5 wt% so that the ratio in terms of solid content was 5 wt% with respect to the pulp, and a pulp composition was prepared. The pulp-containing water-dispersible oil-resistant agent was put into an automatic mold forming machine to produce a pulp mold. When the pulp mold was subjected to a practical oil resistance test at 65°C, the result was 4 points. Table 2 shows the results of temperature variable X-ray diffraction measurement of the solid component obtained by removing the liquid medium from the water-dispersible oil-resistant agent.

[0137] [Example 4] 2 g of HNP-51 (manufactured by Nippon Seiro Co., Ltd.) as wax, 0.18 g of benzalkonium chloride, and 17.8 g of water were mixed to obtain an aqueous dispersion. After heating this aqueous dispersion to 85°C, it was treated with an ultrasonic homogenizer for 20 minutes to obtain an oil-resistant agent in aqueous dispersion form. The obtained oil-resistant agent in aqueous dispersion form exhibited the following properties. Median diameter D50: 0.75 μm Volume ratio of particles of 100 μm or more: 0% Volume ratio of particles of 10 μm or more: 5% Charge density: 80 μeq / g The oil-resistant agent in aqueous dispersion form was added to an aqueous pulp slurry with a concentration of 0.5 wt% so that the ratio to the pulp was 5 wt% in terms of solid content, and a pulp composition was prepared. The pulp-containing oil-resistant agent in aqueous dispersion form was put into an automatic mold forming machine to produce a pulp mold. When the pulp mold was subjected to a practical oil resistance test at 65°C, the result was 4 points. Table 2 shows the results of temperature-variable X-ray diffraction measurement of the solid component obtained by removing the liquid medium from the oil-resistant agent in aqueous dispersion form.

[0138] [Example 5] 2 g of HNP-51 (manufactured by Nippon Seiro Co., Ltd.) as wax, 0.05 g of cationic starch, 0.04 g of abietic acid derivative (rosin 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 an oil-resistant agent in aqueous dispersion form. The obtained oil-resistant agent in aqueous dispersion form exhibited the following properties. Median diameter D50: 0.6 μm Volume ratio of particles of 100 μm or more: 0% Volume ratio of particles of 10 μm or more: 0.4% Charge density: 16 μeq / g Using the obtained oil-resistant agent in aqueous dispersion form, in the same manner as in Example 1, a pulp composition was prepared and a pulp mold was produced. When the pulp mold was subjected to a practical oil resistance test at 65°C, the result was 4 points. Table 2 shows the results of temperature-variable X-ray diffraction measurement of the solid component obtained by removing the liquid medium from the oil-resistant agent in aqueous dispersion form.

[0139] [Example 6] 2 g of HNP-51 (manufactured by Nippon Seiro Co., Ltd.) as wax, 0.10 g of cationic starch, 0.04 g of abietic acid derivative (rosin 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 an oil-resistant agent in aqueous dispersion. The obtained oil-resistant agent in aqueous dispersion showed the following properties. Median diameter D50: 0.26 μm Volume ratio of particles of 100 μm or more: 0% Volume ratio of particles of 10 μm or more: 0.1% Charge density: 39 μeq / g Using the obtained oil-resistant agent in aqueous dispersion, a pulp composition was prepared and a pulp mold was produced in the same manner as in Example 1. When the pulp mold was subjected to a practical oil resistance test at 65°C, it was 4 points.

[0140] [Comparative Example 1] 2 g of Paraffin Wax-115 (manufactured by Nippon Seiro Co., Ltd.) as wax, 0.2 g of polyethylene oxide alkyl ether (alkyl having 6 to 16 carbon atoms, HLB: 7), and 17.8 g of water were mixed to obtain an aqueous dispersion. After heating this aqueous dispersion to 85°C, it was treated with an ultrasonic homogenizer for 20 minutes to obtain an oil-resistant agent in aqueous dispersion. The obtained oil-resistant agent in aqueous dispersion showed the following properties. Median diameter D50: 0.9 μm Volume ratio of particles of 100 μm or more: 0% Volume ratio of particles of 10 μm or more: 10% Charge density: 22 μeq / g The oil-resistant agent in aqueous dispersion was added to an aqueous pulp slurry having a concentration of 0.5 wt% so that the ratio to the pulp was 5 wt% in terms of solid content, and a pulp composition was prepared. The pulp-containing oil-resistant agent in aqueous dispersion was put into an automatic mold forming machine to produce a pulp mold. When the pulp mold was subjected to a practical oil resistance test at 65°C, it was 0 points. Table 2 shows the results of temperature variable X-ray diffraction measurement of the solid component obtained by removing the liquid medium from the water-dispersible oil-resistant agent.

[0141] [Comparative Example 2] As the wax, 2 g of Paraffin Wax-120 (manufactured by Nippon Seiro Co., Ltd.), 0.2 g of polyethylene oxide alkyl ether (alkyl carbon number 6 - 16, HLB: 7), and 17.8 g of water were mixed to obtain an aqueous dispersion. After heating this aqueous dispersion to 85°C, it was treated with an ultrasonic homogenizer for 20 minutes to obtain a water-dispersible oil-resistant agent. The obtained water-dispersible oil-resistant agent showed the following properties. Median diameter D50: 0.9 μm Volume occupancy ratio of particles of 100 μm or more: 0% Volume occupancy ratio of particles of 10 μm or more: 11% Charge density: 21 μeq / g The water-dispersible oil-resistant agent was added to an aqueous pulp slurry with a concentration of 0.5 wt% so that the ratio in terms of solid content was 5 wt% with respect to the pulp, and a pulp composition was prepared. The pulp-containing water-dispersible oil-resistant agent was put into an automatic mold forming machine to produce a pulp mold. When the pulp mold was subjected to a practical oil resistance test at 65°C, the result was 0 points. Table 2 shows the results of temperature variable X-ray diffraction measurement of the solid component obtained by removing the liquid medium from the water-dispersible oil-resistant agent.

Table 1

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 H-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 oil-resistant agent according to Claim 1 or 2, wherein the wax is a petroleum wax.

4. The oil-resistant agent according to Claim 1 or 2, wherein the wax is at least one selected from the group consisting of paraffin wax and microcrystalline wax.

5. The oil-resistant agent according to Claim 1 or 2, wherein the melting point of the wax is 55°C or more.

6. The oil-resistant agent according to Claim 1 or 2, wherein the oil-resistant agent is an aqueous dispersion.

7. The oil-resistant agent contains a dispersant, The oil-resistant agent according to Claim 1 or 2, wherein the dispersant is at least one selected from the group consisting of a nonionic dispersant, an anionic dispersant, and a cationic dispersant.

8. The oil-resistant agent is an aqueous dispersion, The oil-resistant agent contains a dispersant, The oil-resistant agent according to Claim 1 or 2, wherein 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.

9. The oil-resistant agent according to Claim 1 or 2, wherein the charge density is -600 μeq / g or more and 600 μeq / g or less.

10. The oil-resistant agent contains a liquid medium, 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 Claim 1 or 2.

11. The oil-resistant agent according to Claim 1 or 2, which is for pulp products.

12. The oil-resistant agent according to Claim 11, wherein the pulp product is a product for food contact.

13. The oil-resistant agent according to Claim 11, wherein the oil-resistant agent is for internal addition.

14. A pulp composition containing the oil-resistant agent according to Claim 1 or 2 and a pulp base material.

15. A pulp product obtained by treating a pulp base material with the oil-resistant agent according to Claim 1 or 2.

16. A method for manufacturing a pulp product, which includes a step of treating a pulp base material with the oil-resistant agent according to Claim 1 or 2.

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