Oil-resistant agent

Abstract

To provide a novel oil-resistant agent that can impart oil resistance to a substrate (especially a pulp substrate). [Solution] An oil-resistant agent containing wax, wherein the wax 1 An oil-resistant agent in which the integral ratio [integral value B] / [integral value A] between the integral value [integral value A] of signals observed in the chemical shift range of 0.79 ppm to 0.93 ppm in the H-NMR spectrum and the integral value [integral value B] of signals observed in the chemical shift range of 1.05 ppm to 1.47 ppm is 9 or greater.

Description

Technical Field

[0001] The present disclosure relates to release agents, particularly oil-resistant agents.

Background Art

[0002] Patent Document 1 discloses a paper base material for a deoxidizing 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] [[ID=​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​The oil-resistant agent according to item 1, wherein in a 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 a measurement temperature of 25°C and the maximum peak intensity [A60°C] at a measurement temperature of 60°C in the region where 2θ is 15° or more and 30° or less is 0.3 or more. [Section 3] The oil-resistant agent according to item 1 or 2, wherein the wax is petroleum wax. [Section 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. [Section 5] An oil-resistant agent according to any one of claims 1 to 4, wherein the melting point of the wax is 55°C or higher. [Section 6] The oil-resistant agent according to any one of claims 1 to 5, wherein the oil-resistant agent is an aqueous dispersion. [Section 7] The oil-resistant agent includes 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 nonionic dispersants, anionic dispersants, and cationic dispersants. [Section 8] The oil-resistant agent is an aqueous dispersion, The oil-resistant agent includes a dispersant, The oil resistant agent according to any one of items 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. [Section 9] An oil-resistant agent according to any one of items 1 to 8, wherein the charge density is -600 μeq / g or more and 600 μeq / g or less. [Section 10] The oil-resistant agent comprises a liquid medium, An oil-resistant agent according to any one of items 1 to 9, wherein, in a 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 a measurement temperature of 25°C and the maximum peak intensity [A60°C] at a measurement temperature of 60°C in the region where 2θ is 15° to 30° is 0.3 or more. [Section 11] An oil-resistant agent for use in pulp products, as described in any one of items 1 to 10. [Section 12] The oil-resistant agent according to item 11, wherein the pulp product is a food contact product. [Section 13] The oil-resistant agent according to item 11 or 12, wherein the oil-resistant agent is for internal use. [Section 14] A pulp composition comprising an oil-resistant agent and a pulp base material as described in any one of items 1 to 13. [Section 15] A pulp product comprising a pulp base material treated with an oil-resistant agent as described in any one of items 1 to 13. [Section 16] A method for producing pulp products, comprising the step of treating a pulp substrate with an oil-resistant agent described in any one of items 1 to 13. [Effects of the Invention]

[0007] According to this disclosure, oil resistance can be imparted to the substrate (particularly the pulp substrate). [Modes for carrying out the invention]

[0008] <Oil repellent (oil-resistant agent)> The repellent agents in this disclosure adhere to a substrate (particularly a pulp substrate) and can impart liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or antifouling properties to the substrate, and can also function as water-resistant agents, oil-resistant agents, water-repellent agents, oil-repellent agents, and / or antifouling agents. The repellent agents in this disclosure are particularly suitable as oil-resistant agents that impart oil resistance to a substrate.

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

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

[0011] The volume abundance of particles 100 μm or larger, as measured by laser diffraction scattering in the repellent of this 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 20% or less, and more preferably 5% or less. The method for achieving such a volume abundance of particles within the above range is not limited, but for example, the particles in the raw material and / or dispersion can be finely ground using a pulverizer or homogenizer.

[0012] The volume abundance of particles 10 μm or larger, as measured by laser diffraction scattering in the compositions of this 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 30% or less, more preferably 15% or less. The method for achieving such a volume abundance of particles within the above range is not limited, but for example, the particles in the raw material and / or dispersion can be micronized using a pulverizer or homogenizer.

[0013] The volume median diameter measured by laser diffraction scattering in the repellent of this 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 embodiment, 0.01 μm or more and 1 μm or less. In this disclosure, volume median diameter refers to the median diameter (D50) in the volume-based particle size distribution measured by laser diffraction scattering.

[0014] The average particle size obtained from scanning electron microscope images of particles obtained by removing the liquid medium from a water-dispersible composition of a repellent agent (e.g., an oil-resistant agent for pulp) of the present disclosure by natural drying at room temperature may be 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.2 μm or more, 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, or 0.6 μm or more, and may also be 10 μm or less, 5 μm or less, 3 μm or less, 1 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, 0.3 μm or less, or 0.2 μm or less, preferably 1 μm or less. To achieve a particle size within the above range, for example, the particles in the raw material and / or dispersion can be finely ground using a pulverizer or homogenizer. Room temperature is defined as 20°C to 30°C, and especially 25°C.

[0015] The ionic charge density in the repellent of this disclosure may be -1000 μeq / g or more, -800 μeq / g or more, -600 μeq / g or more, -500 μeq / g or more, -400 μeq / g or more, -250 μeq / g or more, -100 μeq / g or more, -50 μeq / g or more, -25 μeq / g or more, 0 μeq / g or more, 1 μeq / g or more, 25 μeq / g or more, 50 μeq / g or more, 100 μeq / g or more, 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 also 5000 μeq / g The following values ​​may be 2500 μeq / g or less, 1000 μeq / g or less, 750 μeq / g or less, 600 μeq / g or less, 500 μeq / g or less, 400 μeq / g or less, 350 μeq / g or less, 300 μeq / g or less, 200 μeq / g or less, 100 μeq / g or less, or 50 μeq / g or less, preferably 1000 μeq / g or less, more preferably 500 μeq / g or less, for example 300 μeq / g or less, particularly 100 μeq / g or less, and in a preferred embodiment, it may be -600 μeq / g or more and 600 μeq / g or less, particularly -100 μeq / g or more and 100 μeq / g or less. The ionic charge density in the repellent of this disclosure can be measured, for example, by the following method.

[0016] The anion demand of a sample solution containing 0.1 g / L solids is measured using a particle charge meter (BTG MUTEK PCD-06) with a 1 / 1000 N potassium polyvinylsulfonate solution, and the ion charge density (cation charge density) is calculated from the following formula (1). Alternatively, the cation demand is measured similarly using a polydiallyldimethylammonium chloride solution instead of potassium polyvinylsulfonate, and the ion charge density (anion charge density) is calculated from the following formula (1). Ion charge density (μeq / g) = A / B (1) A: Cation demand or anion demand (μeq / L) B: Sample solution concentration (g / L)

[0017] When the composition contains a liquid medium (for example, when the repellent is an aqueous dispersion), in a temperature-variable X-ray diffraction measurement of the residue after removing the liquid medium from the repellent, the diffraction intensity ratio [A60°C] / [A25°C] between the maximum peak intensity [A25°C] at a measurement temperature of 25°C and the maximum peak intensity [A60°C] at a measurement temperature of 60°C in the region where 2θ is 15° to 30° may be 0.3 or more, 0.4 or more, 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more, or 0.9 or more, preferably 0.5 or more, and may also be 1.2 or less, 1.0 or less, 0.9 or less, 0.8 or less, or 0.7 or less, and in one embodiment it is 0.3 to 1.0, for example 0.5 to 0.9. In the case of a repellent with a high diffraction intensity ratio (for example, above the lower limit above), it contains a component that has a unique crystalline structure even at 60°C. It is presumed that such a structure can effectively achieve the effects of this disclosure. Temperature-variable X-ray diffraction (XRD-DSC) measurements are performed using Cu Kα rays as the light source, cooling to -20°C under a nitrogen atmosphere, then raising the temperature to 25°C or 60°C at a rate of 5°C / min, holding for 5 minutes, and then taking the measurement. RIGAKU's SmartLab can be used as the measurement device. Furthermore, the liquid medium is removed from the repellent by natural drying at room temperature, followed by drying under reduced pressure for 24 hours.

[0018] 〔wax〕 The repellents of this disclosure include waxes, particularly hydrocarbon waxes. The wax may be an organic substance that is solid at room temperature and becomes liquid when heated. For example, the wax may be a hydrocarbon compound or a compound having a hydrocarbon group (e.g., alkyl group) with 6 to 40 carbon atoms.

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

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

[0021] The wax may be in particulate form (powder). 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 sizes are primary particle sizes. Being within the above range can result in excellent particle stability and good liquid repellency. The average particle size can be measured with a microscope (scanning electron microscope). Specifically, a sample of wax particles is observed with a microscope at any magnification. Next, if the particle shape is spherical, its diameter will be considered as the particle size; if it is non-spherical, the average of the longest and shortest diameters will be considered as the particle size. The particle size of all particles present in the field of view will be measured, and the field of view will be moved and the particle size measured again. By repeating this process, the particle size will be measured at more than 100 points, and the average value of these measurements will be 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 wax above the lower limit, good liquid repellency (especially oil repellency) can be imparted to the substrate. The HD contact angle is the static contact angle of the wax with respect to the spin-coated film, and is obtained by dropping 2 μL of HD onto the spin-coated film and measuring the contact angle 1 second after dropping.

[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 above the lower limit, good liquid repellency (especially water repellency) can be imparted to the substrate. The water contact angle is the static contact angle of the wax with respect to the spin-coated film, and is obtained by dropping 2 μL of water onto the spin-coated film and measuring the contact angle 1 second after the drop.

[0024] The wax may be low molecular weight (for example, molecular weight of 1000 or less, or 500 or less) or high molecular weight. If the wax is high molecular weight, 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, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 100000 or less, 7500 or less, 5000 or less, or 3000 or less.

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

[0026] wax 1The integral ratio [integral value B] / [integral value A] between the integral value of the signal observed in the chemical shift range of 0.79 ppm to 0.93 ppm in the 1H-NMR spectrum [integral value A] and the integral value of the signal observed in the chemical shift range of 1.05 ppm to 1.47 ppm [integral value B] may be 9 or more, 9.5 or more, 10 or more, 10.5 or more, 11 or more, 11.5 or more, 12 or more, 12.5 or more, 13 or more, 13.5 or more, or 14 or more, preferably 9.5 or more, and may also be 25 or less, 22 or less, 20 or less, 18 or less, 16 or less, 14 or less, or 12 or less, and in one embodiment it is 9 to 20, for example 9.5 to 14. In the case of waxes with a high integral ratio, for example above the lower limit, the abundance of methylene hydrogen is greater than the abundance of methyl hydrogen, and a structure with fewer hydrocarbon branching structures may be obtained. It is presumed that such a structure will allow the effects of this disclosure to be achieved effectively. 1 ¹H-NMR measurements are performed on solution samples obtained by dissolving wax in deuterated chloroform.

[0027] In temperature-variable X-ray diffraction measurements of wax, the diffraction intensity ratio [A60°C] / [A25°C] between the maximum peak intensity [A25°C] at a measurement temperature of 25°C and the maximum peak intensity [A60°C] at a measurement temperature of 60°C in the region where 2θ is 15° to 30° is 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, and in one embodiment it is 0.3 to 1.0, for example 0.5 to 0.9. In the case of wax with a high diffraction intensity ratio, for example above the lower limit, it has a unique crystal structure even at 60°C. It is presumed that the effects of this disclosure can be well achieved with such a structure. Temperature-variable X-ray diffraction (XRD-DSC) measurements are performed using Cu Kα rays as the light source, cooling to -20°C under a nitrogen atmosphere, then raising the temperature to 25°C or 60°C at a rate of 5°C / min, holding for 5 minutes, and then taking the measurement. RIGAKU's SmartLab can be used as the measurement device.

[0028] [Types of wax, etc.] Examples of waxes include mineral waxes (petroleum waxes) such as paraffin wax, microcrystalline wax, montane wax, ozokerite wax, ceresin wax, and petrolatum wax; and synthetic waxes such as Fischer-Tropsch wax, polyethylene wax, and polypropylene wax, with paraffin wax or microcrystalline wax being preferred. The wax in this disclosure may be a hydrocarbon wax, preferably a linear 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% or more by weight, 0.5% or more by weight, 1% or more by weight, 3% or more by weight, 5% or more by weight, 10% or more by weight, 20% or more by weight, 30% or more by weight, 50% or more by weight, 70% or more by weight, or 80% or more by weight, and may also be 95% or less by weight, 90% or less by weight, 80% or less by weight, 70% or less by weight, 60% or less by weight, 50% or less by weight, 40% or less by weight, 30% or less by weight, 20% or less by weight, 10% or less by weight, 5% or less by weight, or 3% or less by weight. Wax may also be used alone as a repellent.

[0030] [Dispersant] The repellent in this disclosure may include 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] The dispersant may be either an organic dispersant or an inorganic dispersant, or a combination of both.

[0032] Organic dispersants may be used as dispersants. Organic dispersants can be classified into nonionic dispersants, anionic dispersants, cationic dispersants, and amphoteric dispersants, and the term "organic dispersant" may refer to surfactants.

[0033] The dispersant may be non-fluorinated.

[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 (e.g., molecular weight 2000 or less, particularly 10000 or less) or high molecular weight (e.g., molecular weight 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, 100000 or less, 7500 or less, 50000 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] Examples of ethers are compounds having an oxyalkylene group (preferably a polyoxyethylene group).

[0038] Examples of esters are esters of alcohols and fatty acids. Examples of alcohols are 1-30 valencies (especially 2-10 valencies) with 1-50 carbon atoms (especially 10-30 carbon atoms) (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids with 2-50 carbon atoms, especially 5-30 carbon atoms.

[0039] Examples of ester ethers are compounds formed by adding an alkylene oxide (especially ethylene oxide) to an ester of an alcohol and a fatty acid. Examples of alcohols are 1-30 valencies (especially 2-10 valencies) with 1-50 carbon atoms (especially 3-30 carbon atoms) (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids with 2-50 carbon atoms, especially 5-30 carbon atoms.

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

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

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

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

[0044] 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, etc. 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 [In the formula, 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),​​​​​​​​​​​​​​​The carbon atoms have 8 to 20 carbon atoms, and are more preferably 10 to 18 carbon atoms. 1 Preferred specific examples include the octyl group, nonyl group, trimethylnonyl group, lauryl group, tridecyl group, oleyl group, and stearyl group. R 2 Examples include the propylene group and the butylene group. In nonionic dispersants, p may be a number greater than or equal to 3 (e.g., 5 to 200). q may be a number greater than or equal to 2 (e.g., 5 to 200). That is, -(R 2 O) q - may form a polyoxyalkylene chain. The nonionic dispersant may be a polyoxyethylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) in the center. Examples of hydrophobic oxyalkylene chains include oxypropylene chains, oxybutylene chains, and styrene chains, but oxypropylene chains are preferred among these.

[0047] Specific examples of nonionic dispersants include ethylene oxide and hexylphenol, isooctatylphenol, hexadecanol, oleic acid, and alkanes (C 12 -C 16 ) Thiol, sorbitan monofatty acid (C7-C 19 ) or alkyl (C 12 -C 18 This includes condensation products with amines, sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, lecithin derivatives, etc. Examples of nonionic dispersants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene polyoxybutylene alkyl ethers, polyoxyethylene polyoxypropylene glycol, polyethyleneimine ethoxylate, etc.

[0048] The proportion of polyoxyethylene blocks can be 5 to 80% by weight, for example, 30 to 75% by weight, and especially 40 to 70% by weight, relative to the molecular weight of the nonionic dispersant (copolymer). The average molecular weight of nonionic dispersants is generally 300 to 5,000, for example, 500 to 3,000. The nonionic dispersant may be a single compound or a mixture of two or more compounds. The nonionic dispersant may be a mixture of compounds with an HLB (hydrophilic-hydrophobic balance) of less than 15 (especially 5 or less) and compounds with an HLB of 15 or more. Specifically, it is preferable to select from polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene, polyoxypropylene with an HLB of 1 to 18, or from sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene glycerin fatty acid esters, and polyoxyethylene sorbitan fatty acid esters with an HLB 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 that does not have an amide group.

[0050] The cationic dispersant may be of low molecular weight (e.g., molecular weight of 2000 or less, particularly 10000 or less) or high molecular weight (e.g., molecular weight of 2000 or more). The molecular weight of the cationic dispersant may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 1000000 or less, 750000 or less, 500000 or less, 250000 or less, 100000 or less, 50000 or less, 100000 or less, 7500 or less, 50000 or less, 250000 or less, 750 or less, or 250 or less.

[0051] Cationic dispersants may be aliphatic or aromatic, such as ammonium salts (e.g., quaternary ammonium salts). Cationic dispersants may also be oxyethylene-added ammonium salts. Specifically, examples include amine salt type dispersants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazoline; quaternary ammonium salt type dispersants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzalkonium chloride, and benzethonium chloride; and polymeric cationic dispersants such as polyquaternium-1 to 47. Examples of cationic dispersants include alkylamine salts and quaternary ammonium salts.

[0052] Low molecular weight cationic dispersants are R 21 -N + (-R 22 )(-R 23 )(-R 24 )X - [In the formula, R 21 , R 22 , R 23 and R 24 is hydrogen, or a hydrocarbon group having 1 to 40 carbon atoms. X is an anionic group. It may be a compound represented by R. 21 , R 22 , R 23 and -R 24 Specific examples of X include alkyl groups (e.g., methyl group, butyl group, stearyl group, palmityl group) and aromatic groups (e.g., benzyl group, phenyl group). Specific examples of X include halogens (e.g., chlorine) and acids (e.g., hydrochloric acid, acetic acid). Examples of cationic dispersants include monoalkyltrimethylammonium salts (alkyl group with 4 to 40 carbon atoms) and benzalkonium chloride.

[0053] Specifically, low-molecular-weight cationic dispersants have the formula: R 1 p -N +R 2 q X - [In the formula, R 1 is C12 or higher (for example, C 12 ~C 50 ) is a linear and / or branched aliphatic (saturated and / or unsaturated) group, R 2 The elements are H or C1-C4 alkyl groups, benzyl groups, and polyoxyethylene groups (number of oxyethylene groups, for example, 1 (particularly 2, especially 3) to 50) (CH3 and C2H5 are particularly preferred). X is a halogen atom (e.g., chlorine), or a C1-C4 fatty acid salt, or a C1-C4 sulfonate. p is either 1 or 2, q is either 2 or 3, and p + q = 4. It may be an ammonium salt represented by R. 1 The number of carbon atoms can be 12 to 50, for example, 12 to 30.

[0054] Low molecular weight cationic dispersants may include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydropolyoxyethylene)ammonium chloride, benzyldodecyldi(hydropolyoxyethylene)ammonium chloride, N-[2-(diethylamino)ethyl]oleamide hydrochloride, etc.

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

[0056] [Anionic dispersant] The dispersant may contain an anionic dispersant. The anionic dispersant may be an anionic surfactant. The dispersant does not have to contain an anionic dispersant.

[0057] The anionic dispersant may be of low molecular weight (e.g., molecular weight 2000 or less, particularly 10000 or less) or 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, 100000 or less, 7500 or less, 50000 or less, 250000 or less, 750 or less, 750 or less, or 250 or less.

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

[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 (e.g., molecular weight 2000 or less, especially 10000 or less) or high molecular weight (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, 100000 or less, 7500 or less, 50000 or less, 250000 or less, 750 or less, or 250 or less.

[0061] Examples of amphoteric dispersants include alanines, imidazolinium betaines, amide betaines, and betaine acetate. Specifically, these include lauryl betaine, stearyl betaine, laurylcarboxymethylhydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, and fatty acid amidopropyldimethylaminoacetic acid betaine.

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

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

[0064] Examples of inorganic dispersants include polyvalent metal phosphates such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, and hydroxyapatite; carbonates such as calcium carbonate and magnesium carbonate; silicates such as calcium metasilicate; sulfates such as calcium sulfate and barium sulfate; and hydroxides such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide.

[0065] [Amount of dispersant] The amount of dispersant may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, per 100 parts by weight of 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 media] The repellent in this disclosure may include a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The repellent may be a dispersion or a solution. The repellent in this disclosure is preferably an aqueous dispersion.

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

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

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

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

[0071] 〔silicone〕 The repellent agent in this disclosure may include silicone (polyorganosiloxane). By including silicone, it is possible to achieve good liquid repellency in addition to good texture and durability.

[0072] As the silicone, known silicones can be used. Examples of silicones include polydimethylsiloxane and modified silicones (amino-modified, epoxy-modified, carboxy-modified, methylhydrogen silicones, etc.). The silicone may also be a silicone wax having waxy properties. 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 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more per 100 parts by weight of 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 repellent agent of this disclosure may contain an organic acid. Any known organic acid can be used. Preferred organic acids include carboxylic acids, sulfonic acids, sulfinic acids, etc., with carboxylic acids being particularly preferred. Examples of carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid, etc., with formic acid or acetic acid being particularly preferred. In this disclosure, one organic acid may be used, or two or more may be used in combination. For example, formic acid and acetic acid may be used in combination.

[0076] [Amount of organic acids] The amount of organic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more per 100 parts by weight of 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 organic acid may be adjusted so that the pH of the repellent is 3 to 10, for example 5 to 9, and especially 6 to 8. The repellent may be acidic (pH 7 or less, for example 6 or less).

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

[0078] [Amount of inorganic acid] The amount of inorganic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more per 100 parts by weight of 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 inorganic acid may be adjusted so that the pH of the repellent is 3 to 10, for example 5 to 9, and especially 6 to 8. The repellent may be acidic (pH 7 or less, for example 6 or less).

[0079] [Hardening agent] The repellent agents of this disclosure may contain a curing agent (an active hydrogen-reactive compound or an active hydrogen-containing compound). If the repellent agent is for paper (for example, an oil-resistant agent for paper), it does not need to contain a curing agent.

[0080] [Other ingredients] The repellent agent may contain other components besides those listed above. Examples of other components include polysaccharides, flocculants, yield enhancers, coagulants, binder resins, anti-slip agents, sizing agents, paper strength enhancers, fillers, antistatic agents, preservatives, UV absorbers, antibacterial agents, deodorizers, and fragrances. These may be used individually or in combination of two or more. In addition to the above-mentioned components, other components include other water-repellent and / or oil-repellent agents, dispersants, texture modifiers, softeners, flame retardants, paint fixatives, wrinkle inhibitors, drying speed modifiers, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, insect repellents, defoamers, shrinkage inhibitors, wrinkle inhibitors, shape-retaining agents, drape-retaining agents, ironing improvers, whitening agents, whitening agents, fabric softening clay, color transfer inhibitors such as polyvinylpyrrolidone, polymer dispersants, stain removers, scum dispersants, fluorescent whitening agents such as 4,4-bis(2-sulfostyryl)biphenyldisodium (Chinopearl CBS-X, manufactured by Ciba Specialty Chemicals), dye fixatives, and color-fading inhibitors such as 1,4-bis(3-aminopropyl)piperazine. In addition, enzymes such as cellulase, amylase, protease, lipase, and keratinase can be used as stain removers and fiber surface modifiers; silk protein powder can be used as a foam inhibitor and to impart the texture and functionality of silk, such as moisture absorption and release properties; surface modifiers or emulsified dispersions thereof (e.g., K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical), hydrolyzed silk liquid (Jomo), Silkgen G Solubble S (Ichimaru Falcos)); and anti-fouling agents (e.g., nonionic polymer compounds consisting of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units (e.g., FR627 manufactured by Go-o Chemical Industry), SRC-1 manufactured by Clariant Japan, etc.) can be incorporated. These may be used alone or in combination of two or more. The components may be appropriately determined depending on the application of the repellent.

[0081] [Amount of other ingredients] The individual or total amounts of the other components may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, per 100 parts by weight of 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 this disclosure comprises wax and a pulp substrate. The pulp composition in this disclosure may have excellent oil resistance.

[0083] The pulp composition in this disclosure is obtained by adding wax to a pulp substrate. The pulp composition may also be obtained by treating the pulp substrate with a wax-containing repellent, where the amount and composition of the repellent may be adjusted so that each component is in a desired amount. Each component that may be included in the repellent may be added to the pulp composition separately as an additive.

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

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

[0086] [Pulp-based material] The pulp composition includes a pulp base material. The pulp base material is composed of pulp, which may be wood pulp, non-wood pulp, recycled paper pulp, etc.

[0087] [Wood pulp] Wood pulp includes coniferous kraft pulp obtained from genera such as fir and pine, and hardwood kraft pulp obtained from genera such as acacia, eucalyptus, beech, and aspen (e.g., poplar). Examples of coniferous kraft pulp include unbleached coniferous kraft pulp (NUKP), bleached coniferous pulp (NBKP), semi-bleached coniferous kraft pulp (NSBKP), and sulfite coniferous pulp. Examples of hardwood kraft pulp include unbleached hardwood kraft pulp (LUKP), bleached hardwood kraft pulp (LBKP), semi-bleached hardwood kraft pulp (LSBKP), and sulfite hardwood pulp. The pulp used may be used alone or in combination. In addition to kraft pulp, there are also softwood kraft pulp and hardwood kraft pulp, as well as mechanical pulps such as stone ground pulp (SGP), pressure stone ground pulp (PGW), refiner ground pulp (RGP), thermo ground pulp (TGP), chemiground pulp (CGP), crushed wood pulp (GP), and thermomechanical pulp (TMP). Furthermore, recycled paper pulp includes disintegrated recycled paper pulp, disintegrated and deinked recycled paper pulp, or disintegrated, deinked and bleached recycled paper pulp, which are manufactured from brown recycled paper, recycled kraft envelopes, recycled magazines, recycled newspapers, recycled flyers, recycled office paper, recycled corrugated cardboard, recycled white recycled paper, recycled Kent paper, recycled imitation paper, recycled land certificates, etc.

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

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

[0090] [Pulp fiber width] From the viewpoint of improving oil resistance, the average fiber diameter of the pulp is preferably 5 μm or more, more preferably 10 μm or more, even more preferably 15 μm or more, and also preferably 50 μm or less, more preferably 40 μm or less, and even more preferably 30 μm or less.

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

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

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

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

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

[0096] 〔wax〕 The pulp composition contains wax, particularly hydrocarbon wax. For details on the types of wax, refer to the description of wax in the section on <Repellents>.

[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 relative to the pulp base material, preferably 0.5% by weight or more, and may also be 25% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, for example, 15% by weight or less, 5.0% by weight or less, or 3.0% by weight or less.

[0098] The wax may be applied as an external additive to the surface of a pulp substrate (e.g., paper, paper containers, pulp molded products, etc.), and the amount of wax contained in the coating layer formed by the external additive treatment is 0.01 g / m². 2 More than 0.03g / m 2 More than 0.05g / m 2 More than 0.1g / m 2 More than 0.3g / m 2 More than 0.5g / m 2 Above, or 1.0 g / m 2 The above is sufficient, and also 5.0 g / m 2 Below 4.0g / m 2 Below 3.0g / m 2 Below 2.0g / m 2 Below 1.0g / m 2 Below 0.5g / m 2 Below 0.3g / m 2 The following, or 0.1 g / m² 2 The following is acceptable:

[0099] [Dispersant] The pulp composition may contain a dispersant. For details on the types of dispersants, refer to the explanation of dispersants in the section on <Water-repellent agents>.

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

[0101] [Paper strengthening agent] The pulp composition may contain a paper strength agent. Examples of paper strength agents include: Polyacrylamide-based paper strengthening agents such as cationic polyacrylamide, anionic polyacrylamide, and amphoteric polyacrylamide; Polysaccharide-based paper strengthening agents such as starch, enzyme-modified starch, thermochemically modified starch, oxidized starch, esterified starch, etherified starch (e.g., hydroxyethylated starch), aldehyde-modified starch, cationized starch, starch, xanthan gum, karaya gum, welan gum, guar gum, pectin, tamarind gum, carrageenan, chitosan, gum arabic, locust bean gum, cellulose, alginic acid, agar, dextran, cellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, chitin nanofibers, cellulose nanofibers, and pullulan, and modified polysaccharides thereof (e.g., modified polysaccharides into which hydroxyl groups or cationic groups have been introduced); Polyamide-based paper strengthening agents such as polyamide resins, polyamine resins, polyamide-polyamine resins, polyamide-epichlorohydrin resins, polyamide-polyamine-epichlorohydrin resins, polyamide-polyurea-formaldehyde resins, and epoxidized polyamide resins; Urea / melamine-based paper strengthening 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 terminally alkyl-modified polyvinyl alcohol; Examples include styrene-butadiene copolymers, polyvinyl acetate, vinyl chloride-vinyl acetate copolymers, polyvinyl chloride, polyvinylidene chloride, polyacrylic acid esters, fatty acid diamides, polyethyleneimine resins, and ketone aldehyde resins. In this disclosure, polyacrylamide-based paper strength agents, polysaccharide-based paper strength agents, or polyamide-based paper strength agents are preferred.

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

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

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

[0105] [Other additives] In addition to the above, the pulp composition may also contain other additives such as known paper-use chemicals used in the manufacture of pulp products, including fixatives (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 defoamers.

[0106] [Amount of other additives] The amounts of other additives may be 0.01% by weight or more, 0.1% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, respectively, relative to the pulp base material, or 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, 3% by weight or less, or 1% by weight or less.

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

[0108] The substrates treated with the treatment agents in this disclosure are not limited, but are preferably fibrous substrates, and may be particularly textile substrates or pulp substrates, and especially pulp substrates.

[0109] Examples of fiber base materials include natural animal and plant fibers such as cotton, linen, 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 fibers, carbon fibers, and asbestos fibers; or blends thereof. Fiber products include woven fabrics, knitted fabrics, and nonwoven fabrics; fabrics in the form of clothing (e.g., water-repellent clothing, e.g., raincoats) and carpets; however, fibers, yarns, and intermediate fiber products (e.g., slivers or rovings) in their pre-fabric state may also be treated.

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

[0111] When the substrate is glass, the manufactured glass product may be an optical component. A layer (or film), such as a hard coat layer or an anti-reflective layer, may be formed on the surface (outermost layer) of the glass substrate. Either a single-layer anti-reflective layer or a multi-layer anti-reflective layer may be used for the anti-reflective layer. Examples of inorganic materials that can be used for the anti-reflective layer include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, CeO2, MgO, Y2O3, SnO2, MgF2, and WO3. These inorganic materials may be used individually or in combination of two or more (for example, as a mixture). When a multi-layer anti-reflective layer is used, it is preferable to use SiO2 and / or SiO for the outermost layer. When the article to be manufactured is an optical glass component for a touch panel, a thin film using a transparent electrode, such as indium tin oxide (ITO) or indium zinc oxide, may be present on part of the surface of the substrate (glass). Furthermore, the substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomizing film layer, a hard coating film layer, a polarizing film, a phase difference film, and a liquid crystal display module, depending on its specific specifications.

[0112] [Method of manufacturing pulp products] The pulp products (paper products) in this disclosure can be obtained by treating a pulp substrate with a wax-containing repellent to obtain a pulp composition, and then subjecting that composition to processing steps such as drying, heating, and molding as necessary.

[0113] The repellent agent in this disclosure can be applied to a pulp substrate by conventionally known methods as a treatment agent (particularly a surface treatment agent). The treatment method may involve diluting the repellent agent in this disclosure by dispersing it in an organic solvent or water as needed, and then applying it to the interior and / or surface of the pulp substrate by known methods such as immersion coating, spray coating, or foam coating, followed by drying. The dilution ratio may be appropriately changed depending on the concentration and application of the repellent agent, but may be 3 to 2000 times, for example, 10 to 100 times. After drying, a pulp product with the solid components of the repellent agent attached is obtained. Furthermore, if necessary, it may be applied together with a suitable crosslinking agent and curing may be performed.

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

[0115] As a method for processing pulp substrates, an internal processing method in which a repellent is added to the pulp substrate before papermaking (e.g., in the form of a pulp slurry) or an external processing method in which a repellent is applied to the pulp substrate after papermaking (e.g., a pulp product) can be used. Examples of internal processing methods include mixing and immersion, and may include a step of adding a repellent to the pulp slurry and stirring and mixing it. Examples of external processing methods include spraying, coating, immersion, and foam coating, and specifically include a pound-type two-roll size press, a gate-roll type, and a rod-metering size press. The processing may be either external or internal. For example, when the pulp substrate is paper, the paper may be coated, or the solution may be attached to or sprayed onto the paper, or it may be mixed with the pulp slurry before papermaking. When the pulp substrate is a fibrous material, examples of processing methods include padding, immersion, spraying, and coating. For padding treatment, for example, methods using padding equipment described on pages 396-397 of the Dictionary of Textile Dyeing and Processing (published in 1963 by Nikkan Kogyo Shimbun) and pages 256-260 of Color Dyeing Chemistry III (published in 1975 by Jikkyo Shuppan Co., Ltd.) can be used. For coating treatment, for example, methods using coating machines described on pages 473-477 of the General Catalog of Dyeing and Finishing Equipment (published in 1981 by Senryo-sha) can be used. For immersion treatment, for example, methods using batch-type dyeing machines described on pages 196-247 of the General Catalog of Dyeing and Finishing Equipment (published in 1981 by Senryo-sha) can be used, and liquid flow dyeing machines, air flow dyeing machines, drum dyeing machines, winch dyeing machines, washer dyeing machines, cheese dyeing machines, etc. can be used. For spray treatment, for example, methods using air sprays that atomize the treatment liquid with compressed air and spray it, or air sprays using a liquid pressure atomization method can be used.

[0116] The processing method may be an internal additive treatment in which a repellent agent is added to the pulp slurry before papermaking. The internal additive treatment may include, but is not limited to, one or more of the following steps: adding a repellent agent to the pulp slurry and stirring and mixing it; dewatering the pulp composition prepared in the first step by suction through a mesh-like body of a predetermined shape to deposit the pulp composition and form a pulp molded intermediate; and molding and drying the pulp molded intermediate using a heated mold to obtain a pulp molded product. After simple drying at room temperature or high temperature, the processed paper may optionally be heat-treated depending on the properties of the paper. The heat treatment temperature may be 150°C or higher, 180°C or higher, or 210°C or higher, and may be 300°C or lower, 250°C or lower, or 200°C or lower, and may be particularly 80°C to 180°C. By performing heat treatment in such a temperature range, excellent oil resistance and other properties can be obtained. The pulp substrate, which has undergone internal additive treatment, may be further treated externally with a repellent, and additional waxes or repellents may be applied to the surface.

[0117] The processing method may be an external additive treatment in which a repellent is applied to the pulp substrate after papermaking. Size presses for external additive treatment can also be classified as follows depending on the application method. One application method is the so-called pound-type two-roll size press, in which a coating liquid (sizing liquid) is supplied to the nip portion formed by passing paper between two rubber rolls, creating a coating liquid reservoir called a pound, and the sizing liquid is applied to both sides of the paper by passing the paper through this reservoir. Other application methods are the gate-roll type and the rod-metering size press, in which the sizing liquid is applied by a surface transfer type. In the pound-type two-roll size press, the sizing liquid easily penetrates into the interior of the paper, while in the surface transfer type, the sizing liquid components tend to remain on the surface of the paper. Compared to the pound-type two-roll size press, the surface transfer type allows the coating layer to remain on the surface of the paper more easily, and the coating layer formed on the surface is greater than that of the pound-type two-roll size press. In this disclosure, performance can be imparted to the paper even when the former pound-type two-roll size press is used. Paper processed in this manner can exhibit excellent oil resistance and other properties after simple drying at room temperature or high temperature, and optionally, depending on the properties of the paper, undergo heat treatment up to 300°C, for example, up to 200°C, and particularly within a temperature range of 80°C to 180°C.

[0118] Specific examples of pulp products include paper, paper containers, pulp molded articles, food packaging materials, food containers, gypsum board base paper, coated base paper, medium-grade paper, general liners and cores, neutral pure white roll paper, neutral liners, rust-preventive liners and metal interleaving paper, kraft paper, neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper, and neutral information paper. Suitable examples of pulp products include food packaging materials and food containers, and for example, pulp products for food contact applications, particularly pulp molded articles for food contact applications.

[0119] Although embodiments have been described above, it should be understood that various modifications to the form and details are possible without departing from the spirit and scope of the claims. [Examples]

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

[0121] The examination procedure is as follows:

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

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

[0124] [Median diameter D50] The results were obtained by measuring water-dispersible oil-resistant agents using a laser diffraction / scattering device.

[0125] [Ionic charge density] The ionic charge density in the oil-resistant agent of this disclosure can be measured, for example, by the following method. The anion demand of a sample solution containing 0.1 g / L solids is measured using a particle charge meter (BTG MUTEK PCD-04) with a 1 / 1000 N potassium polyvinylsulfonate solution, and the ion charge density (cation charge density) is calculated from the following formula (1). Alternatively, the cation demand is measured similarly using a polydiallyldimethylammonium chloride solution instead of potassium polyvinylsulfonate, and the ion charge density (anion charge density) is calculated from the following formula (1). Ion charge density (μeq / g) = A / B (1) A: Cation demand or anion demand (μeq / L) B: Sample solution concentration (g / L)

[0126] [Preparation of pulp molds] An automatic mold molding machine was used to form the pulp mold. At the bottom, a mesh structure was placed on top of a metal pulp mold with numerous suction holes, and at the top, a metal tank was placed. A mixture of pulp slurry and a water-dispersible oil-resistant agent was placed in the upper metal tank. From the side of the pulp mold opposite the mesh structure, the pulp-containing aqueous composition was sucked and dewatered through the pulp mold and mesh structure using a vacuum pump, and the solid components (pulp, etc.) contained in the pulp-containing aqueous composition were deposited on the mesh structure to obtain a pulp mold intermediate. Next, the obtained pulp mold intermediate was dried from above and below under a pressure of 0.05 to 5 MPa using a metal male-female mold heated to 60 to 250°C. This produced a pulp mold product molded into the shape of a container.

[0127] [Practical oil resistance test at 65℃] The pulp molds were pre-treated by storing them for 12 hours under conditions of 23°C and 50% humidity. 100 ml of 65°C corn oil was poured into the pulp molds, and after standing at room temperature for 45 minutes, the corn oil was removed from the pulp molds, and the degree of oil penetration was evaluated. The following evaluation values ​​were set based on the degree of penetration. 5: No stains on the inside 4: Stain on the inside. No stain on the reverse side. 3: There is a stain on the inside. There is a slight seepage on the reverse side. 2: There is a stain on the inside. The stain has seeped through to the back over less than 50% of the area. 1: There is a stain on the inside. The stain has seeped through to the back, covering more than 50% but less than 100% of the area. 0: Staining across the entire 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). DSC measurements were performed under a nitrogen atmosphere, after cooling to -20°C, and then measuring the endothermic peaks observed during the subsequent heating process to 180°C at a rate of 10°C / min. When multiple endothermic peaks appeared, the highest temperature peak was defined as the maximum endothermic peak, and its peak top was defined as the maximum endothermic peak temperature. This maximum endothermic peak temperature corresponds to the melting point of the wax. The amount of endothermic heat was calculated by determining the heat within a 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 (XRD) using RIGAKU's SmartLab. Cu Kα rays were used as the light source. For variable temperature XRD (XRD-DSC) measurements, the wax was cooled to -20°C under a nitrogen atmosphere, then heated to 25°C or 60°C at a rate of 5°C / min, held for 5 minutes, and then measured. The full width at half maximum of the peak was defined as the width of the 2θ of the peak at half the intensity of the baseline and the peak top. The diffraction intensity ratio [A60℃ / A25℃] was calculated as follows: At a measurement temperature of 25°C, the intensity of the diffraction intensity maximum in the region where 2θ is 15° to 30° was defined as [Peak Intensity A25°C]. Similarly, at a measurement temperature of 60°C, the intensity of the diffraction intensity maximum in the region where 2θ is 15° to 30° was defined as [Peak Intensity A60°C]. The diffraction intensity ratio [A60°C / A25°C] was calculated by dividing [Peak Intensity A60°C] by [Peak Intensity A25°C] as shown in the following formula. Diffraction intensity ratio [A60℃ / A25℃] = [Peak intensity A60℃] / [Peak intensity A25℃]

[0130] [wax 1 [H-NMR Spectrometry] wax 1 The integral ratio [integral value B] / [integral value A] between the integral value of signals observed in the chemical shift range of 0.79 ppm to 0.93 ppm in the H-NMR spectrum [integral value A] and the integral value of signals observed in the chemical shift range of 1.05 ppm to 1.47 ppm [integral value B] was measured by the following method. The wax was dissolved in deuterated chloroform (containing tetramethylsilane) to prepare the measurement sample. Then, a nuclear magnetic resonance spectrometer (JEOL° 400 MHz) was used. 1 The 1H-NMR spectrum was measured. The chemical shift criterion was set so that the tetramethylsilane (TMS) peak in the obtained spectrum was 0 ppm. Phase correction was performed using first-order phase correction in the TMS chemical shift region and second-order phase correction in the deuterated chloroform chemical shift region to adjust the signal flatness. The integral value of the signal in the chemical shift range of 0.79 ppm to 0.93 ppm was calculated and set to 6, which was designated as [Integral Value A]. Next, the integral value of the signal observed in the chemical shift range of 1.05 ppm to 1.47 ppm was calculated and designated as [Integral Value B]. [Integral Value B] / [Integral Value A] was calculated by dividing [Integral Value B] by [Integral Value A].

[0131] [Differential scanning calorimetry of solid components obtained by removing the liquid medium from an oil-resistant agent] The maximum endothermic peak temperature, melting point, crystallization temperature, and glass transition temperature of the solid component obtained by removing the liquid medium from the oil resistant agent were calculated by differential scanning calorimetry (DSC). The liquid medium was removed from the oil resistant agent by natural drying at room temperature, followed by drying under reduced pressure for 24 hours. DSC measurements were performed under a nitrogen atmosphere, cooling to -20°C, and then measuring the endothermic peaks observed during the subsequent heating process to 180°C at a rate of 10°C / min. When multiple endothermic peaks appeared, the highest-temperature endothermic peak was defined as the maximum endothermic peak, and its peak top was defined as the maximum endothermic peak temperature. The amount of endothermic heat was calculated by determining the heat quantity within a range of ±10°C of the endothermic peak temperature.

[0132] [Temperature-variable X-ray diffraction measurement of solid components obtained by removing the liquid medium from oil-resistant agents] The crystalline state of the solid component obtained by removing the liquid medium from the oil-resistant agent was measured by X-ray diffraction (XRD) using RIGAKU's SmartLab. Cu Kα rays were used as the light source. Variable temperature XRD (XRD-DSC) measurements were performed under a nitrogen atmosphere, after cooling to -20°C, then raising the temperature at 5°C / min to 25°C or 55°C, holding for 5 minutes, and then measuring. The full width at half maximum of the peak was defined as the width of the 2θ of the peak at half the intensity of the baseline and the peak top. The diffraction intensity ratio [A55℃ / A25℃] was calculated as follows: At a measurement temperature of 25°C, the intensity of the diffraction intensity maximum in the region where 2θ is 15° to 30° was defined as [Peak Intensity A25°C]. Similarly, at a measurement temperature of 60°C, the intensity of the diffraction intensity maximum in the region where 2θ is 15° to 30° was defined as [Peak Intensity A60°C]. The diffraction intensity ratio [A60°C / A25°C] was calculated by dividing [Peak Intensity A60°C] by [Peak Intensity A25°C] as shown in the following formula. Diffraction intensity ratio [A60℃ / A25℃] = [Peak intensity A60℃] / [Peak intensity A25℃] The liquid medium was removed from the oil-resistant agent by natural drying at room temperature, followed by drying under reduced pressure for 24 hours.

[0133] [Evaluation Example 1] As waxes, we used 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.) for differential scanning calorimetry, temperature-variable X-ray diffraction, and 1 1H-NMR spectroscopy was performed. The maximum endothermic peak temperature in differential scanning calorimetry, and the peak intensity [A25°C] at a measurement temperature of 25°C and [A60°C] at a measurement temperature of 60°C in temperature-variable X-ray diffraction, and the diffraction intensity ratio [A60°C / A25°C] calculated from these. 1 The results of the 1H-NMR spectrum measurements are shown in Table 1.

[0134] [Example 1] A water dispersion was obtained by mixing 2 g of HNP-3 (manufactured by Nippon Seiro Co., Ltd.) as a wax, 0.2 g of polyethylene oxide alkyl ether (alkyl with 6 to 16 carbon atoms, HLB: 7), and 17.8 g of water. 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 exhibited the following properties. Median diameter D50: 0.9 μm Volume abundance of particles larger than 100 μm: 0% Volume abundance of particles larger than 10 μm: 9% Charge density: 21 μeq / g A pulp composition was prepared by adding a water-dispersible oil-resistant agent to a 0.5 wt% aqueous pulp slurry at a ratio of 5 wt% relative to the pulp in terms of solid content. The pulp-containing water-dispersible oil-resistant agent was then fed into an automatic mold molding machine to produce pulp molds. When the pulp mold was subjected to a practical oil resistance test at 65°C, it scored 4 points. Table 2 shows the results of temperature-variable X-ray diffraction measurements of the solid component obtained by removing the liquid medium from the water-dispersible oil-resistant agent.

[0135] [Example 2] A water dispersion was obtained by mixing 2g of HNP-10 (manufactured by Nippon Seiro Co., Ltd.) as a wax, 0.2g of polyethylene oxide alkyl ether (alkyl with 6-16 carbon atoms, HLB: 7), and 17.8g of water. 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 exhibited the following properties. Median diameter D50: 0.9 μm Volume abundance of particles larger than 100 μm: 0% Volume abundance of particles larger than 10 μm: 11% Charge density: 19 μeq / g A pulp composition was prepared by adding a water-dispersible oil-resistant agent to a 0.5 wt% aqueous pulp slurry at a ratio of 5 wt% relative to the pulp in terms of solid content. The pulp-containing water-dispersible oil-resistant agent was then fed into an automatic mold molding machine to produce pulp molds. When the pulp mold was subjected to a practical oil resistance test at 65°C, it scored 4 points. Table 2 shows the results of temperature-variable X-ray diffraction measurements of the solid component obtained by removing the liquid medium from the water-dispersible oil-resistant agent.

[0136] [Example 3] A water dispersion was obtained by mixing 2g of HNP-51 (manufactured by Nippon Seiro Co., Ltd.) as a wax, 0.2g of polyethylene oxide alkyl ether (alkyl with 6-16 carbon atoms, HLB: 7), and 17.8g of water. 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 exhibited the following properties. Median diameter D50: 0.8 μm Volume abundance of particles larger than 100 μm: 0% Volume abundance of particles larger than 10 μm: 12% Charge density: 25 μeq / g A pulp composition was prepared by adding a water-dispersible oil-resistant agent to a 0.5 wt% aqueous pulp slurry at a ratio of 5 wt% relative to the pulp in terms of solid content. The pulp-containing water-dispersible oil-resistant agent was then fed into an automatic mold molding machine to produce pulp molds. When the pulp mold was subjected to a practical oil resistance test at 65°C, it scored 4 points. Table 2 shows the results of temperature-variable X-ray diffraction measurements of the solid component obtained by removing the liquid medium from the water-dispersible oil-resistant agent.

[0137] [Example 4] A water dispersion was obtained by mixing 2g of HNP-51 (manufactured by Nippon Seiro Co., Ltd.), 0.18g of benzalkonium chloride, and 17.8g of water as wax. 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 exhibited the following properties. Median diameter D50: 0.75 μm Volume abundance of particles larger than 100 μm: 0% Volume abundance of particles larger than 10 μm: 5% Charge density: 80 μeq / g A pulp composition was prepared by adding a water-dispersible oil-resistant agent to a 0.5 wt% aqueous pulp slurry at a ratio of 5 wt% relative to the pulp in terms of solid content. The pulp-containing water-dispersible oil-resistant agent was then fed into an automatic mold molding machine to produce pulp molds. When the pulp mold was subjected to a practical oil resistance test at 65°C, it scored 4 points. Table 2 shows the results of temperature-variable X-ray diffraction measurements of the solid component obtained by removing the liquid medium from the water-dispersible oil-resistant agent.

[0138] [Example 5] A water-dispersible oil-resistant agent was obtained by mixing 2g of HNP-51 (manufactured by Nippon Seiro Co., Ltd.) as a wax, 0.05g of cationic starch, 0.04g of abietic acid derivative (rosin-type sizing agent), 0.04g of formic acid, 0.04g of acetic acid, and 7.83g of water, heating to 95°C, and then treating with an ultrasonic homogenizer for 20 minutes. The obtained water-dispersible oil-resistant agent exhibited the following properties. Median diameter D50: 0.6 μm Volume abundance of particles larger than 100 μm: 0% Volume abundance of particles larger than 10 μm: 0.4% Charge density: 16 μeq / g Using the obtained water-dispersible oil-resistant agent, a pulp composition was prepared in the same manner as in Example 1, and a pulp mold was manufactured. When the pulp mold was subjected to a practical oil resistance test at 65°C, it scored 4 points. Table 2 shows the results of temperature-variable X-ray diffraction measurements of the solid component obtained by removing the liquid medium from the water-dispersible oil-resistant agent.

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

[0140] [Comparative Example 1] A water dispersion was obtained by mixing 2g of Paraffin Wax-115 (manufactured by Nippon Seiro Co., Ltd.), 0.2g of polyethylene oxide alkyl ether (alkyl with 6-16 carbon atoms, HLB: 7), and 17.8g of water. This water dispersion was heated to 85°C and then treated with an ultrasonic homogenizer for 20 minutes to obtain a water-dispersible oil-resistant agent. The obtained water-dispersible oil-resistant agent exhibited the following properties. Median diameter D50: 0.9 μm Volume abundance of particles larger than 100 μm: 0% Volume abundance of particles larger than 10 μm: 10% Charge density: 22 μeq / g A pulp composition was prepared by adding a water-dispersible oil-resistant agent to a 0.5 wt% aqueous pulp slurry at a ratio of 5 wt% relative to the pulp in terms of solid content. The pulp-containing water-dispersible oil-resistant agent was then fed into an automatic mold molding machine to produce pulp molds. When the pulp mold was subjected to a practical oil resistance test at 65°C, it scored 0 points. Table 2 shows the results of temperature-variable X-ray diffraction measurements of the solid component obtained by removing the liquid medium from the water-dispersible oil-resistant agent.

[0141] [Comparative Example 2] As a wax, 2g of Paraffin Wax-120 (manufactured by Nippon Seiro Co., Ltd.), 0.2g of polyethylene oxide alkyl ether (alkyl with 6-16 carbon atoms, HLB: 7), and 17.8g 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 exhibited the following properties. Median diameter D50: 0.9 μm Volume abundance of particles larger than 100 μm: 0% Volume abundance of particles larger than 10 μm: 11% Charge density: 21 μeq / g A pulp composition was prepared by adding a water-dispersible oil-resistant agent to a 0.5 wt% aqueous pulp slurry at a ratio of 5 wt% relative to the pulp in terms of solid content. The pulp-containing water-dispersible oil-resistant agent was then fed into an automatic mold molding machine to produce pulp molds. When the pulp mold was subjected to a practical oil resistance test at 65°C, it scored 0 points. Table 2 shows the results of temperature-variable X-ray diffraction measurements 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 wax １ An oil-resistant agent in which the integral ratio [integral value B] / [integral value A] between the integral value [integral value A] of signals observed in the chemical shift range of 0.79 ppm to 0.93 ppm in the H-NMR spectrum and the integral value [integral value B] of signals observed in the chemical shift range of 1.05 ppm to 1.47 ppm is 9 or greater.

2. The oil-resistant agent according to claim 1, wherein in a 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 a measurement temperature of 25°C and the maximum peak intensity [A60°C] at a measurement temperature of 60°C in the region where 2θ is 15° or more and 30° or less is 0.3 or more.

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 higher.

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 includes 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 nonionic dispersants, anionic dispersants, and cationic dispersants.

8. The oil-resistant agent is an aqueous dispersion, The oil-resistant agent includes 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 comprises a liquid medium, The oil-resistant agent according to claim 1 or 2, wherein, in a 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 a measurement temperature of 25°C and the maximum peak intensity [A60°C] at a measurement temperature of 60°C in the region where 2θ is 15° or more and 30° or less is 0.3 or more.

11. An oil-resistant agent according to claim 1 or 2, for use in pulp products.

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

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

14. A pulp composition comprising the oil-resistant agent and the pulp base material according to claim 1 or 2.

15. A pulp product comprising a pulp base material treated with the oil-resistant agent described in claim 1 or 2.

16. A method for producing a pulp product, comprising the step of treating a pulp substrate with an oil-resistant agent according to claim 1 or 2.

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