Wax and oil-resistant agent for pulp

Abstract

This wax is a wax particle used in an oil-resistant agent for pulp, and has a median diameter (D50) of 0.01-1 μm, as measured by a laser diffraction scattering method, and this oil-resistant agent for pulp is a water-dispersible composition, contains a wax and a dispersant, and has a median diameter (D50) of 0.01-1 μm. Consequently, provided is a novel wax or oil-resistant agent for pulp, with which oil resistance can be imparted to a pulp substrate.

Description

Oil-resistant agent for wax and pulp

[0001] The present disclosure relates to oil-proofing agents for waxes and pulp.

[0002] Patent Document 1 discloses a masking tape that does not repel paint from the coated surface by using an aqueous emulsion containing a specific paraffin wax as a release treatment agent.

[0003] JP 2011-116836 A

[0004] Patent Document 1 neither describes nor suggests the use of a wax having a specific particle size for pulp, nor does it describe or suggest the development of oil resistance.

[0005] An object of the present disclosure is to provide a novel wax or oil-proofing agent for pulp that can impart oil resistance to a pulp base material.

[0006] The present disclosure includes the following aspects: [Item 1] Wax particles for use in an oil-proofing agent for pulp, the wax having a volume median diameter (D50) of 0.01 μm or more and 1 μm or less. [Item 2] The wax according to Item 1, which is a petroleum wax. [Item 3] The wax according to Item 1 or 2, which is at least one wax selected from the group consisting of paraffin wax and microcrystalline wax. [Item 4] The wax according to any one of Items 1 to 3, which is for internal addition. [Item 5] The wax according to any one of Items 1 to 4, which is at least one wax selected from the group consisting of paraffin wax and microcrystalline wax, is for internal addition, and has a volume median diameter (D50) of 0.1 μm or more and 1 μm or less. [Item 6] An oil-proofing agent for pulp, comprising the wax according to any one of Items 1 to 5. [Item 7] An oil-proofing agent for pulp that is a water-dispersible composition, comprising a wax and a dispersant, and having a volume median diameter (D50) of 0.01 μm or more and 1 μm or less. [Item 8] The oil-proofing agent for pulp according to Item 7, wherein the particles obtained by removing the liquid medium by natural drying at room temperature have an average particle size of 0.01 μm or more and 1 μm or less, as determined from a scanning electron microscope image. [Item 9] The oil-proofing agent for pulp according to Item 7 or 8, wherein the wax is a petroleum wax. [Item 10] The oil-proofing agent for pulp according to any one of Items 7 to 9, wherein the wax is at least one wax selected from the group consisting of paraffin wax and microcrystalline wax. [Item 11] The oil-proofing agent for pulp according to any one of Items 7 to 10, wherein the charge density is -600 μeq / g or more and 100 μeq / g or less. [Item 12] The oil-proofing agent for pulp according to any one of Items 7 to 11, which contains an organic acid or an inorganic acid.[Item 13] The oil-proofing agent for pulp according to any one of Items 7 to 12, wherein the wax is at least one selected from the group consisting of paraffin wax and microcrystalline wax, the dispersant is at least one selected from the group consisting of nonionic dispersants, anionic dispersants, and cationic dispersants, the pulp additive contains an organic acid, the amount of the dispersant is 1 part by weight to 50 parts by weight per 100 parts by weight of the wax, the volume median diameter (D50) is 0.1 μm to 1 μm, the volume abundance ratio of particles of 100 μm or larger is 20% or less, the volume abundance ratio of particles of 10 μm or larger is 40% or less, and the charge density is -400 μeq / g to 400 μeq / g. [Item 14] A method for producing a pulp product, comprising a step of treating a pulp base material with the oil-proofing agent for pulp according to any one of Items 6 to 13. [Item 15] A pulp product treated with the oil-proofing agent for pulp according to any one of Items 6 to 13. [Item 16] The pulp product according to Item 15, which is a pulp molded article for food contact applications.

[0007] According to the present disclosure, oil resistance can be imparted to a pulp base material.

[0008] <Repellent Agent> The repellent agent in the present disclosure adheres to a substrate (particularly a pulp substrate) and can impart liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or stain resistance, to the substrate, and can also function as a water-resistant agent, oil-resistant agent, water repellent, oil repellent, and / or stain resistance agent. For example, the repellent agent in the present disclosure can be used as an oil-resistant agent or an oil-resistant agent for pulp.

[0009] The repellent of the present disclosure may contain wax as an active ingredient (wax will be described in detail separately under [Wax]). Wax may be used as a repellent by itself, or may be used as a repellent in combination with other ingredients as described below.

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

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

[0012] The volumetric abundance ratio of particles of 10 μm or larger in the repellent agent of the present disclosure, as measured by laser diffraction scattering, may be 0.05% or larger, 0.1% or larger, 0.3% or larger, 0.5% or larger, 1% or larger, 1.5% or larger, 3% or larger, 4% or larger, 5% or larger, or 10% or larger, or may be 50% or smaller, 30% or smaller, 20% or smaller, 15% or smaller, 10% or smaller, 5% or smaller, 3% or smaller, or 1.5% or smaller, and preferably 25% or smaller, 15% or smaller, or 10% or smaller. The method for achieving the volumetric abundance ratio of particles of 1 μm or larger, as measured by laser diffraction scattering, within the above range is not limited, and may be, for example, by micronizing the particles in the raw material and / or dispersion using a grinder, homogenizer, or the like.

[0013] The volume median diameter of the repellent agent of the present disclosure, as measured by a laser diffraction scattering method, may be 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.2 μm or more, 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, or 0.6 μm or more, or may be 10 μm or less, 5 μm or less, 3 μm or less, 1 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, 0.3 μm or less, or 0.2 μm or less, preferably 1 μm or less. In the present disclosure, the volume median diameter refers to the median diameter (D50) in a volume-based particle size distribution measured by a laser diffraction scattering method.

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

[0015] The ionic charge density in the repellent of the present disclosure may be −1000 μeq / g or more, −800 μeq / g or more, −600 μeq / g or more, −500 μeq / g or more, −400 μeq / g or more, −250 μeq / g or more, −100 μeq / g or more, −50 μeq / g or more, −25 μeq / g or more, 0 μeq / g or more, 1 μeq / g or more, 25 μeq / g or more, 50 μeq / g or more, 100 μeq / g or more, 200 μeq / g or more, preferably −600 μeq / g or more, for example −400 μeq / g or more. The ionic charge density may be 5000 μeq / g or less, 2500 μeq / g or less, 1000 μeq / g or less, 750 μeq / g or less, 500 μeq / g or less, 400 μeq / g or less, 350 μeq / g or less, 300 μeq / g or less, 200 μeq / g or less, 100 μeq / g or less, or 50 μeq / g or less, preferably 1000 μeq / g or less, more preferably 500 μeq / g or less, for example 300 μeq / g or less. In particular, the ionic charge density of the repellent of the present disclosure is preferably -600 μeq / g or more and 100 μeq / g or less.

[0016] When the ionic charge density of the repellent has a negative value, for example, less than -10 μeq / g, it can impart electric charge repulsion to the dispersion, improving the stability of the aqueous dispersion. In addition, when the substrate has a positive charge, it can enhance the interaction with the substrate, improving the oil resistance when the repellent is applied to the substrate. When the repellent has a negative charge, its ionic charge density may be less than -20 μeq / g, less than -50 μeq / g, less than -75 μeq / g, or less than -100 μeq / g.

[0017] When the ionic charge density of the repellent is, for example, in the range of −10 μeq / g or more and less than 10 μeq / g, aggregation can be suppressed when mixed with a highly charged drug.

[0018] When the ionic charge density of the repellent has a positive value, for example, 10 μeq / g or more, it can impart charge repulsion to the dispersion, improving the stability of the aqueous dispersion. In addition, when the substrate has a negative charge, it can enhance the interaction with the substrate, improving the oil resistance when treated on the substrate. When the repellent has a positive charge, its ionic charge density may be 20 μeq / g or more, 50 μeq / g or more, 75 μeq / g or more, 100 μeq / g or more, or 150 μeq / g or more.

[0019] The ionic charge density of the repellent of the present disclosure can be measured, for example, by the following method.

[0020] The anion demand of a sample liquid with a solid content of 0.1 g / L is measured using a 1 / 1000 N potassium polyvinyl sulfonate solution with a particle charge meter (MUTEK PCD-04 manufactured by BTG), and the ionic charge density (cationic charge density) is calculated using the following formula (1). Alternatively, the cation demand is measured in the same manner using a polydiallyldimethylammonium chloride solution instead of potassium polyvinyl sulfonate, and the ionic charge density (anionic charge density) is calculated using the following formula (1). Ionic charge density (μeq / g) = A / B (1) A: cation demand or anionic demand (μeq / L) B: sample liquid concentration (g / L)

[0021] [Wax] The repellent of the present disclosure may contain wax. The wax may be an organic substance that is solid at room temperature and becomes liquid when heated, and may be, for example, a hydrocarbon compound or a compound having a hydrocarbon group (e.g., an alkyl group) having 6 to 40 carbon atoms.

[0022] The waxes of the present disclosure can be adhered to a substrate (particularly a pulp substrate) to impart liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or stain resistance to the substrate.

[0023] The wax may be a compound having a monovalent hydrocarbon group having 1 to 40 carbon atoms, which may have a substituent, or a monovalent polysiloxane group. From the viewpoint of improving liquid repellency, the wax may have a hydrocarbon group having 6 to 40 carbon atoms (for example, an alkyl group).

[0024] [Properties of Wax, etc.] Possible properties of wax are shown below.

[0025] The wax may be in a particulate (powder) form. The average particle size of the wax may be 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.2 μm or more, 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, or 0.6 μm or more, and may be 10 μm or less, 5 μm or less, 3 μm or less, 1 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, 0.3 μm or less, or 0.2 μm or less, preferably 1 μm or less. The above particle size is the primary particle size. A particle size within the above range can provide excellent particle stability and good liquid repellency. The average particle size can be measured using a microscope (scanning electron microscope). Specifically, a wax particle sample is observed under a microscope at an arbitrary magnification. Next, if the particle shape is spherical, the diameter is considered to be the particle size, and if the particle shape is non-spherical, the average value of the longest and shortest diameters is considered to be the particle size. By measuring the particle size of all particles present within the field of view, and then moving the field of view and measuring the particle size again, particle sizes are measured at 100 or more points, and the average value is considered to be the average particle size.

[0026] The wax in the present disclosure is preferably wax particles having a predetermined particle volume abundance ratio or median diameter (D50) measured by a laser diffraction scattering method. The laser diffraction scattering method for wax in the present disclosure is performed in a dry state or a wet state using a medium that does not dissolve the wax (e.g., water). The volume abundance ratio and median diameter (D50) of the wax measured by the laser diffraction scattering method and the volume abundance ratio and median diameter (D50) of the repellent (water-dispersible composition) measured by the laser diffraction scattering method are usually not significantly different, and the difference may be ±30% or less, ±20% or less, ±10% or less, or ±5% or less.

[0027] The volumetric abundance ratio of particles of 100 μm or larger in the wax of the present disclosure, as measured by laser diffraction scattering, may be 0.1% or larger, 0.3% or larger, 0.5% or larger, 1% or larger, 1.5% or larger, 3% or larger, 4% or larger, 5% or larger, or 10% or larger, or may be 50% or smaller, 30% or smaller, 20% or smaller, 15% or smaller, 10% or smaller, 5% or smaller, 3% or smaller, or 1.5% or smaller, and preferably 25% or smaller, 15% or smaller, or 10% or smaller. The method for achieving the volumetric abundance ratio of particles of 1 μm or larger, as measured by laser diffraction scattering, within the above range is not limited, and may be, for example, by using a grinder, homogenizer, or the like to micronize the particles in the raw material and / or dispersion.

[0028] The volumetric abundance ratio of particles of 10 μm or larger in the wax of the present disclosure, as measured by laser diffraction scattering, may be 0.1% or larger, 0.3% or larger, 0.5% or larger, 1% or larger, 1.5% or larger, 3% or larger, 4% or larger, 5% or larger, or 10% or larger, or may be 50% or smaller, 30% or smaller, 20% or smaller, 15% or smaller, 10% or smaller, 5% or smaller, 3% or smaller, or 1.5% or smaller. The method for achieving the volumetric abundance ratio of particles of 1 μm or larger, as measured by laser diffraction scattering, within the above range is not limited, and may be, for example, by using a grinder, homogenizer, or the like to micronize the particles in the raw material and / or dispersion.

[0029] The volume median diameter of the wax of the present disclosure, as measured by a laser diffraction scattering method, may be 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.2 μm or more, 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, or 0.6 μm or more, or may be 10 μm or less, 5 μm or less, 3 μm or less, 1 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, 0.3 μm or less, or 0.2 μm or less, preferably 1 μm or less. In the present disclosure, the volume median diameter refers to the median diameter (D50) in a volume-based particle size distribution measured by a laser diffraction scattering method.

[0030] The HD (n-hexadecane) contact angle of the wax may be 10° or more, 20° or more, 25° or more, 30° or more, 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 60° or more, or 65° or more, preferably 25° or more, more preferably 30° or more, and may be 100° or less, 90° or less, or 75° or less. When the wax has an HD contact angle equal to or greater than the above lower limit, it can impart good liquid repellency (particularly oil repellency) to the substrate. The HD contact angle is the static contact angle of the wax with respect to a spin-coated film, and is obtained by dropping 2 μL of HD onto the spin-coated film and measuring the contact angle one second after the drop lands.

[0031] The water contact angle of the wax may be 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 65° or more, 75° or more, 85° or more, 90° or more, or 100° or more, and may be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. When the wax has a water contact angle equal to or greater than the above lower limit, it can impart good liquid repellency (particularly water repellency) to the substrate. The water contact angle is the static contact angle of the wax with respect to a spin-coated film, and is obtained by dropping 2 μL of water on the spin-coated film and measuring the contact angle 1 second after the drop lands.

[0032] The wax may be a low molecular weight (e.g., a molecular weight of 1000 or less, or 500 or less) or a polymer. When the wax is a polymer, its weight average molecular weight may be 1000 or more, 3000 or more, 5000 or more, 7500 or more, 10000 or more, 30000 or more, 100,000 or more, 300,000 or more, or 500,000 or more, or 10,000,000 or less, 7,500,000 or less, 5,000,000 or less, 3,000,000 or less, 1,000,000 or less, 750,000 or less, 500,000 or less, 300,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 3 ...,000 or less, 75000 or less, 50000 or less, or 3,000 or less.

[0033] The melting point of the wax may be 30°C or higher, 40°C or higher, 60°C or higher, 80°C or higher, 100°C or higher, or 120°C or higher, preferably 40°C or higher, 50°C or higher, 60°C or higher, 70°C or higher, or 80°C or higher, and may be 250°C or lower, 225°C or lower, 200°C or lower, 150°C or lower, 130°C or lower, 120°C or lower, 110°C or lower, 100°C or lower, 80°C or lower, or 50°C or lower, for example, 150°C or lower, or 100°C or lower. The melting point of the wax may be measured in accordance with JIS K 2235-1991.

[0034] [Wax Structure, etc.] The wax in the present disclosure does not necessarily have any group selected from the group consisting of a fluoroalkyl group having 8 or more carbon atoms, a perfluoroalkyl group having 8 or more carbon atoms, a fluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group, a fluoroalkyl group, and a fluorine atom. Even if the wax does not contain these fluorine-containing groups, it can impart liquid repellency to a substrate.

[0035] The wax may be a hydrocarbon compound, or a compound having a monovalent hydrocarbon group having from 1 to 40 carbon atoms, which may have a substituent, or a monovalent polysiloxane group. From the viewpoint of improving liquid repellency, the wax may be a hydrocarbon compound or a compound having a hydrocarbon group (e.g., an alkyl group) having from 6 to 40 carbon atoms.

[0036] (Monovalent Hydrocarbon Group Which May Have a Substitute) The wax may have a monovalent hydrocarbon group Which may have a substituent.

[0037] The hydrocarbon group may be a monovalent hydrocarbon group having from 1 to 40 carbon atoms. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be branched, cyclic, or linear, and is more preferably linear.

[0038] The number of carbon atoms in the hydrocarbon group may be 1 or more, 3 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, preferably 6 or more, 10 or more, 12 or more, or 16 or more, and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, 25 or less, or 20 or less.

[0039] The hydrocarbon group may have a substituent, but is preferably unsubstituted. Examples of the substituent include -OR' and -N(R'). ２ , —COOR′, and halogen atoms (wherein R′, in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the substituted hydrocarbon group, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less. For example, the hydrocarbon group may have 1 to 3 (e.g., 1) —OR′ (particularly —OH) as a substituent (e.g., other than at the terminal).

[0040] (Monovalent Polysiloxane Group) The wax may have a monovalent polysiloxane group. Like the (monovalent) hydrocarbon group, the (monovalent) polysiloxane group can impart liquid repellency to the substrate.

[0041] The polysiloxane group has the following formula: —[—Si(R ｓ ) ２ -O-] ａ - [wherein, R ｓ is independently in each occurrence a hydrocarbon group or a reactive group having 1 to 40 carbon atoms, and a is an integer of 5 or more and 10,000 or less.

[0042] R ｓis a hydrocarbon group having 1 to 40 carbon atoms or a reactive group.

[0043] Examples of hydrocarbon groups having 1 to 40 carbon atoms include hydrocarbon groups having 1 to 5 carbon atoms and hydrocarbon groups having 6 to 40 carbon atoms.

[0044] Examples of the hydrocarbon group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and other hydrocarbon groups having 1 to 5 carbon atoms (particularly an aliphatic hydrocarbon group, particularly an alkyl group such as a methyl group or an ethyl group, particularly a methyl group).

[0045] The hydrocarbon group having 6 to 40 carbon atoms may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, preferably an aliphatic hydrocarbon group, and particularly preferably a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be cyclic, linear, or branched, preferably linear. The number of carbon atoms in the hydrocarbon group may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, preferably 10 or more, more preferably 12 or more, and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, more preferably 25 or less.

[0046] Examples of reactive groups include groups having functional groups (e.g., hydroxy groups, amino groups, mercapto groups, epoxy groups, carboxyl groups, halogen-substituted alkyl groups, vinyl groups, (meth)acrylic groups, (meth)acryloyloxy groups, (meth)acrylamide groups, hydrogen atoms directly bonded to silicon atoms, etc.). These functional groups may be directly bonded to the silicon atom, or may be bonded to an organic group directly bonded to the silicon atom. The organic group may be a hydrocarbon group, such as an alkylene group or a divalent aromatic group. The hydrocarbon group may have from 2 to 12 carbon atoms, and the alkylene group preferably has from 2 to 10 carbon atoms. The divalent aromatic group preferably has from 6 to 12 carbon atoms. The reactive group may be a group selected from the group consisting of a hydroxy group, an epoxy ring, a carboxyl group, a (meth)acrylic group, and an amino group, and may be, for example, at least one selected from the group consisting of an epoxy ring, a hydroxy group, a (meth)acrylic group, and a carboxyl group.

[0047] a may be 3 or more, 5 or more, 10 or more, 30 or more, 50 or more, 100 or more, 500 or more, 1000 or more, 2000 or more, or 3000 or more, and is preferably 10 or more, and may be 10,000 or less, 7,500 or less, 5,000 or less, 3,000 or less, 1,500 or less, 1,000 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less, and is preferably 500 or less.

[0048] In the polysiloxane group, R is a hydrocarbon group having 1 to 5 carbon atoms. ｓ The amount of R ｓ It may be 20 mol% or more, 40 mol% or more, 60 mol% or more, or 80 mol% or more, preferably 50 mol% or more, and may be 100 mol% or less, 90 mol% or less, 80 mol% or less, or 70 mol% or less, based on the total of R ｓ With respect to the total number of groups, 50 mol % or more may be methyl groups or ethyl groups (particularly methyl groups).

[0049] In the polysiloxane group, R is a hydrocarbon group having 6 to 40 carbon atoms. ｓ The amount of R ｓand may be 100 mol % or less, 90 mol % or less, 80 mol % or less, or 70 mol % or less, based on the total of

[0050] In the polysiloxane group, reactive groups R ｓ The amount of R ｓ and may be 5 mol % or more, 10 mol % or more, 20 mol % or more, or 30 mol % or more relative to the total of R ｓ may be 50 mol % or less, 40 mol % or less, 30 mol % or less, or 20 mol % or less based on the total of

[0051] R ｓ The groups may be introduced randomly or in blocks, but are preferably introduced randomly.

[0052] The terminal structure of the polysiloxane group is not limited, but may be -OR ｓ , -Si(R ｓ ) ３ etc. The R of the terminal structure ｓ Examples of the reactive group are as described above, and may be, for example, at least one selected from the group consisting of an epoxy ring, a hydroxy group, a (meth)acrylic group, and a carboxyl group.

[0053] The polysiloxane group may have a linker, and the raw material compound and the polysiloxane group may be bonded via a linker. Such a linker may be, but is not limited to, a hydrocarbon group having 1 to 40 (e.g., 1 to 20) carbon atoms which may be interrupted by an oxygen atom, for example, a (poly)oxyalkylene group having 1 to 40 (e.g., 1 to 20) carbon atoms.

[0054] Examples of polysiloxane groups include -[-Si(R ｓ ) ２ -O-] ａ -Si(R ｓ ) ３ -L ｓ１ -[-Si(R ｓ ) ２ -O-] ａ -Si(R ｓ ) ３-L ｓ１ -O-L ｓ１ -[-Si(R ｓ ) ２ -O-] ａ -R ｓ -L ｓ１ -[-Si(R ｓ ) ２ -O-] ａ -Si(R ｓ ) ３ -L ｓ１ -O-L ｓ１ -[-Si(R ｓ ) ２ -O-] ａ -R ｓ -L ｓ１ -[-Si(R ｓ ) ２ -O-] ａ -Si(R ｓ ) ３、 -L ｓ１ -[-Si(R ｓ ) ２ -O-] ａ -R ｓ [In the formula, R ｓ is independently in each occurrence a hydrocarbon group or a reactive group having 1 to 40 carbon atoms, and the terminal R ｓ has one or more reactive groups, and R ｓ 50 mol % or more of the total groups are methyl groups, and L ｓ１ is a hydrocarbon group having 1 to 20 carbon atoms, and a is 5 or more and 10,000 or less. [In the formula, a represents an integer of 0 to 150, b represents an integer of 1 to 150, (a+b) is 5 to 200, and n is an integer of 0 to 36.]

[0055] [Examples of Wax] The wax may be a hydrocarbon compound or a compound having a hydrocarbon group. Examples and preferred ranges of the hydrocarbon group are as described above. For example, the hydrocarbon group may have 6 to 40 carbon atoms.

[0056] Examples of waxes include hydrocarbon waxes (paraffin, polyolefin, etc.), non-hydrocarbon waxes, polymer waxes (vinyl polymer, silicone wax, etc.), etc. Petroleum waxes such as paraffin wax, microcrystalline wax, montan wax, ozokerite wax, ceresin wax, and petrolatum wax, and synthetic waxes such as Fischer-Tropsch wax, polyethylene wax, polypropylene wax, acrylic polymer wax, polytetrafluoroethylene wax, and silicone wax.

[0057] The wax may be a hydrocarbon compound.

[0058] [Amount of Wax] The amount of wax in the repellent may be 0.01% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 50% by weight or more, 70% by weight or more, or 80% by weight or more, and may be 95% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, or 3% by weight or less. Wax alone may be used as the repellent.

[0059] [Dispersant] The repellent of the present disclosure may contain a dispersant. The dispersant may be at least one selected from an organic dispersant and an inorganic dispersant. The dispersant may be at least one selected from an anionic dispersant, a nonionic dispersant, a cationic dispersant, an amphoteric dispersant, and an inorganic dispersant.

[0060] As the dispersant, an organic dispersant and an inorganic dispersant may be used individually, or a combination of an organic dispersant and an inorganic dispersant may be used.

[0061] An organic dispersant may be used as the dispersant. The organic dispersant can be classified into a nonionic dispersant, an anionic dispersant, a cationic dispersant, and an amphoteric dispersant, and the organic dispersant may refer to a surfactant.

[0062] The dispersant may be fluorine-free.

[0063] [Nonionic Dispersant] The dispersant may contain a nonionic dispersant, which may be a nonionic surfactant.

[0064] The nonionic dispersant may be a low molecular weight or a high molecular weight dispersant, and may have a molecular weight of 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may be 100,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0065] Examples of nonionic dispersants include ethers, esters, ester ethers, alkanolamides, polyols and amine oxides.

[0066] An example of an ether is a compound having an oxyalkylene group (preferably a polyoxyethylene group).

[0067] An example of the ester is an ester of an alcohol and a fatty acid. An example of the alcohol is a mono- to trio-hydric (particularly di- to deca-hydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 10 to 30 carbon atoms). An example of the fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0068] An example of an ester ether is a compound in which an alkylene oxide (particularly ethylene oxide) is added to an ester of an alcohol and a fatty acid. An example of an alcohol is a mono- to trio-hydric (particularly di- to deca-hydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms). An example of a fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0069] Examples of alkanolamides are those formed from fatty acids and alkanolamines. The alkanolamides may be monoalkanolamides or dialkanolamines. Examples of fatty acids include saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. The alkanolamines may be alkanols having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, and having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0070] The polyol may be a di- to penta-hydric alcohol having 10 to 30 carbon atoms. The amine oxide may be an oxide (for example, having 5 to 50 carbon atoms) of an amine (secondary amine or preferably tertiary amine).

[0071] The nonionic dispersant is preferably a nonionic dispersant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms in the alkylene group in the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic dispersant is generally preferably 2 to 100.

[0072] 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.

[0073] The nonionic dispersant may be an alkylene oxide adduct of a linear and / or branched aliphatic (saturated and / or unsaturated) group, a polyalkylene glycol ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a sorbitan ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a glycerin ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyglycerin ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a sucrose ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of acetylene glycol, or the like. Among these, those in which the alkylene oxide adduct moiety and the polyalkylene glycol moiety have a structure of polyoxyethylene (POE), polyoxypropylene (POP), or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred. Furthermore, the nonionic dispersant does not have to contain an aromatic group.

[0074] The nonionic dispersant has the formula: １ O-(CH ２ CH ２ O)ｐ - (R ２ O) ｑ -R ３ [In the formula, R １ is an alkyl group having 1 to 22 carbon atoms, or an alkenyl group or acyl group having 2 to 22 carbon atoms, ２ are independently the same or different and are alkylene groups having 3 or more carbon atoms (e.g., 3 to 10), ３ is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms, p is a number of 2 or more, and q is a number of 0 or 1 or more.

[0075] R １ R preferably has 8 to 20 carbon atoms, particularly 10 to 18 carbon atoms. １ Preferred specific examples of R include an octyl group, a nonyl group, a trimethylnonyl group, a lauryl group, a tridecyl group, an oleyl group, and a stearyl group. ２ Examples of the nonionic dispersant are a propylene group and a butylene group. In the nonionic dispersant, p may be a number of 3 or more (for example, 5 to 200). q may be a number of 2 or more (for example, 5 to 200). That is, -(R ２ O) ｑ - may form a polyoxyalkylene chain. The nonionic dispersant may be a polyoxyethylene alkylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) at the center. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, and a styrene chain, with the oxypropylene chain being preferred.

[0076] Specific examples of nonionic dispersants include ethylene oxide and hexylphenol, isooctatylphenol, hexadecanol, oleic acid, alkanes (C １２ -C １６ ) thiol, sorbitan mono fatty acid (C ７ -C １９ ) or alkyl (C １２ -C １８) condensation products with amines, etc., sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, lecithin derivatives, etc. Examples of nonionic dispersants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene polyoxybutylene alkyl ethers, polyoxyethylene polyoxypropylene glycol, polyethyleneimine ethoxylate, etc.

[0077] The proportion of polyoxyethylene blocks can be 5 to 80% by weight, for example 30 to 75% by weight, and particularly 40 to 70% by weight, based on the molecular weight of the nonionic dispersant (copolymer). The average molecular weight of the nonionic dispersant is generally 300 to 5,000, for example 500 to 3,000. The nonionic dispersant may be a single type or a mixture of two or more types. The nonionic dispersant may be a mixture of a compound having an HLB (hydrophilic-hydrophobic balance) of less than 15 (particularly 5 or less) and a compound having an HLB of 15 or more. Specifically, it is preferable to select from polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene, and polyoxypropylenes having an HLB value of 1 to 18, and sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene glycerin fatty acid esters, and polyoxyethylene sorbitan fatty acid esters having an HLB value of less than 7.

[0078] [Cationic Dispersant] The dispersant may contain a cationic dispersant. The cationic dispersant may be a cationic surfactant. The cationic dispersant may be a compound having no amide group.

[0079] The cationic dispersant may be a low molecular weight type (e.g., a molecular weight of 2000 or less, particularly 10,000 or less) or a high molecular weight type (e.g., a molecular weight of 2000 or more). The molecular weight of the cationic dispersant may be 100 or more, 500 or more, 1,000 or more, 2,000 or more, 4,000 or more, or 6,000 or more, and may be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0080] The cationic dispersant may be aliphatic or aromatic, and examples thereof include ammonium salts (e.g., quaternary ammonium salts). The cationic dispersant may be an oxyethylene adduct ammonium salt. Specific examples include amine salt-type dispersants such as alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazolines; quaternary ammonium salt-type dispersants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzalkonium chloride, and benzethonium chloride; and polymer-type cationic dispersants such as Polyquaternium-1 to 47. Examples of cationic dispersants include alkylamine salts and quaternary ammonium salts.

[0081] The low molecular weight cationic dispersant is R ２１ -N ＋ (-R ２２ ) (-R ２３ ) (-R ２４ ) X － [In the formula, R ２１ , R ２２ , R ２３ and R ２４ is hydrogen or a hydrocarbon group having 1 to 40 carbon atoms, and X is an anionic group. ２１ , R ２２ , R ２３ and R ２４Specific examples of X include alkyl groups (e.g., methyl, butyl, stearyl, and palmityl groups) and aromatic groups (e.g., benzyl and phenyl groups). Specific examples of X include halogens (e.g., chlorine) and acids (e.g., hydrochloric acid and acetic acid). Examples of cationic dispersants include monoalkyltrimethylammonium salts (alkyl having 4 to 40 carbon atoms) and benzalkonium chloride.

[0082] Specifically, the low molecular weight cationic dispersant is represented by the formula: １ ｐ -N ＋ R ２ ｑ X － [In the formula, R １ is C12 or more (e.g. C １２ ~C ５０ ) is a linear and / or branched aliphatic (saturated and / or unsaturated) group of the formula R ２ is H or a C1-4 alkyl group, a benzyl group, a polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (particularly 2, particularly 3) to 50) (CH ３ , C ２ H ５ is particularly preferred), and X is a halogen atom (e.g., chlorine), or C １ ~C ４ or a fatty acid salt of C １ ~C ４ where p is 1 or 2, q is 2 or 3, and p+q=4. １ may have 12 to 50 carbon atoms, for example, 12 to 30 carbon atoms.

[0083] Examples of low molecular weight cationic dispersants include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydropolyoxyethylene)ammonium chloride, benzyldodecyldi(hydropolyoxyethylene)ammonium chloride, N-[2-(diethylamino)ethyl]oleamide hydrochloride, and the like.

[0084] The polymeric cationic dispersant may be any of various polymers (e.g., polyquaternium-1 to -47) having a cationic group (e.g., ammonium group, quaternary ammonium group). Examples of the polymeric cationic dispersant include cationic natural products (particularly cationic sugars) such as cationic starch, cationic cellulose (e.g., O-(2-hydroxy-3-(trimethylammonio)propylhydroxyethylcellulose chloride), cationic guar gum, cationic xanthan gum, and chitosan; and polymers of cationic group-containing monomers such as aziridine, vinylimidazole, aminoalkyl methacrylate, N,N,N',N'-tetramethyl-2-butene-1,4-diamine, quaternized dimethylammonium ethyl methacrylate, diallyldimethylammonium chloride, dimethylaminopropylamine, and quaternized vinylimidazole.

[0085] [Anionic Dispersant] The dispersant may contain an anionic dispersant. The anionic dispersant may be an anionic surfactant. The dispersant may not contain an anionic dispersant.

[0086] The anionic dispersant may be a low molecular weight or a high molecular weight dispersant, and may have a molecular weight of 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may have a molecular weight of 100,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0087] Examples of anionic dispersants include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkanesulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfonic acid salts, N-acylamino acid type dispersants, phosphate mono- or diester type dispersants, and sulfosuccinate esters. An example of an anionic dispersant is a carboxylate (e.g., a fatty acid salt).

[0088] [Amphoteric Dispersant] The dispersant may contain an amphoteric dispersant, which may be an amphoteric surfactant.

[0089] The amphoteric dispersant may be a low molecular weight or a high molecular weight dispersant, and may have a molecular weight of 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may have a molecular weight of 100,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0090] Examples of amphoteric dispersants include alanines, imidazolinium betaines, amido betaines, and acetic acid betaine, and specific examples include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylamino acetic acid betaine, and fatty acid amidopropyl dimethylamino acetic acid betaine.

[0091] [Inorganic Dispersant] The dispersant may contain an inorganic dispersant.

[0092] The average primary particle size of the inorganic dispersant may be 5 nm or more, 30 nm or more, 100 nm or more, 1 μm or more, 10 μm or more, or 25 μm or more, and may be 100 μm or less, 50 μm or less, 10 μm or less, 1 μm or less, 500 nm or less, or 300 nm or less. The average primary particle size can be measured, for example, by observation with a microscope (scanning electron microscope or transmission electron microscope). The inorganic dispersant may be hydrophilic particles.

[0093] 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.

[0094] [Amount of Dispersant] The amount of dispersant may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of wax, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less.

[0095] [Liquid Medium] The repellent agent of the present disclosure may contain a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The repellent agent may be a dispersion or a solution. The repellent agent of the present disclosure may contain at least water.

[0096] Examples of organic solvents include esters (e.g., esters having 2 to 40 carbon atoms, specifically, ethyl acetate and butyl acetate), ketones (e.g., ketones having 2 to 40 carbon atoms, specifically, methyl ethyl ketone and diisobutyl ketone), alcohols (e.g., alcohols having 1 to 40 carbon atoms, specifically, isopropyl alcohol), aromatic solvents (e.g., toluene and xylene), and petroleum solvents (e.g., alkanes having 5 to 10 carbon atoms, specifically, naphtha and kerosene). The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent may contain a compound having at least one hydroxy group (e.g., alcohol, polyols such as glycol-based solvents, ethers of polyols (e.g., monoethers), etc.). These may be used alone or in combination.

[0097] [Amount of Liquid Medium] The amount of the liquid medium may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 1 part by weight of the wax.

[0098] The amount of water may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, per part by weight of wax.

[0099] The amount of organic solvent may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 1 part by weight of wax.

[0100] [Silicone] The repellent agent according to the present disclosure may contain silicone (polyorganosiloxane). By containing silicone, it is possible to obtain good texture and durability in addition to good liquid repellency.

[0101] As the silicone, known silicones can be used, and examples of silicones include polydimethylsiloxane and modified silicones (amino-modified, epoxy-modified silicone, carboxy-modified silicone, methylhydrogen silicone, etc.). The silicone may be a silicone wax having wax-like properties. These may be used alone or in combination of two or more.

[0102] The weight average molecular weight of the silicone may be 1,000 or more, 10,000 or more, or 50,000 or more. The weight average molecular weight of the silicone may be 500,000 or less, 2,500,000 or less, 100,000 or less, or 50,000 or less.

[0103] [Amount of Silicone] The amount of silicone may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the wax, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0104] [Organic Acid] The repellent of the present disclosure may contain an organic acid. Known organic acids can be used. Preferred examples of the organic acid include carboxylic acid, sulfonic acid, sulfinic acid, etc., with carboxylic acid being particularly preferred. Examples of the carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid, etc., with formic acid or acetic acid being particularly preferred. In the present disclosure, one type of organic acid may be used, or two or more types may be used in combination. For example, formic acid and acetic acid may be used in combination. Adding an organic acid can improve the stability of the aqueous dispersion.

[0105] [Amount of Organic Acid] The amount of organic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of wax, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less. The amount of organic acid may be adjusted so that the pH of the repellent is 3 to 10, for example, 5 to 9, particularly 6 to 8. The repellent may be acidic (pH 7 or less, for example, 6 or less).

[0106] [Inorganic Acid] The repellent of the present disclosure may contain an inorganic acid. Known inorganic acids can be used. Examples of inorganic acids include hydrogen chloride, hydrogen bromide, hydrogen iodide, nitric acid, boric acid, sulfuric acid, and phosphoric acid. In the present disclosure, one type of inorganic acid may be used, or two or more types may be used in combination. Adding an inorganic acid can improve the stability of the aqueous dispersion.

[0107] [Amount of Inorganic Acid] The amount of inorganic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of wax. The amount of inorganic acid may be adjusted so that the pH of the repellent is 3 to 10, for example, 5 to 9, particularly 6 to 8. The repellent may be acidic (pH 7 or less, for example, 6 or less).

[0108] [Hardening Agent] The repellent of the present disclosure may contain a hardening agent (active hydrogen-reactive compound or active hydrogen-containing compound).

[0109] The curing agent (crosslinking agent) in the repellent agent can cure the agent well. The curing agent may be an active hydrogen-reactive compound or an active hydrogen-containing compound that reacts with active hydrogen or an active hydrogen-reactive group. Examples of active hydrogen-reactive compounds are isocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds, and hydrazide compounds. Examples of active hydrogen-containing compounds are hydroxyl group-containing compounds, amino group-containing compounds, carboxyl group-containing compounds, ketone group-containing compounds, hydrazide compounds, and melamine compounds.

[0110] The curing agent may contain an isocyanate compound. The isocyanate compound may be a polyisocyanate compound. The polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound functions as a crosslinking agent. Examples of polyisocyanate compounds include aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates. The isocyanate compound may be a blocked isocyanate compound (for example, a blocked polyisocyanate compound). The blocked isocyanate compound is a compound in which the isocyanate group of an isocyanate compound is masked with a blocking agent to inhibit reaction.

[0111] Examples of aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate, Aliphatic diisocyanates such as cyanatomethyl caproate, and aliphatic triisocyanates such as lysine ester triisocyanate, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, and 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane. These may be used alone or in combination of two or more.

[0112] Examples of alicyclic polyisocyanates include alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of alicyclic polyisocyanates include 1,3-cyclopentene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), and 1,3,5-triisocyanatocyclohexane. These may be used alone or in combination of two or more.

[0113] Examples of araliphatic polyisocyanates include araliphatic diisocyanates and araliphatic triisocyanates. Specific examples of araliphatic polyisocyanates include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethylxylylene diisocyanate) or a mixture thereof, and 1,3,5-triisocyanatomethylbenzene. These may be used alone or in combination of two or more.

[0114] Examples of aromatic polyisocyanates include aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate or a mixture thereof, 2,4- or 2,6-tolylene diisocyanate or a mixture thereof, triphenylmethane-4,4',4''-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate. These may be used alone or in combination of two or more.

[0115] Examples of the polyisocyanate derivatives include various derivatives of the above-mentioned polyisocyanate compounds, such as dimers, trimers, biurets, allophanates, carbodiimides, uretdiones, uretimines, isocyanurates, and iminooxadiazinediones. These may be used alone or in combination of two or more.

[0116] These polyisocyanates can be used alone or in combination of two or more. As the polyisocyanate compound, it is preferable to use a blocked polyisocyanate compound (blocked isocyanate), which is a compound in which the isocyanate group of a polyisocyanate compound is blocked with a blocking agent. It is preferable to use a blocked polyisocyanate compound because it is relatively stable in solution and can be used in the same solution as the repellent.

[0117] The blocking agent blocks free isocyanate groups. When the blocked polyisocyanate compound is heated to, for example, 100°C or higher, e.g., 130°C or higher, the isocyanate groups are regenerated and can easily react with hydroxyl groups. Examples of blocking agents include phenolic compounds, lactam compounds, aliphatic alcohol compounds, and oxime compounds. The polyisocyanate compounds can be used alone or in combination of two or more.

[0118] An epoxy compound is a compound having an epoxy group. Examples of epoxy compounds include epoxy compounds having a polyoxyalkylene group, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether. A chloromethyl group-containing compound is a compound having a chloromethyl group. An example of a chloromethyl group-containing compound is chloromethyl polystyrene. A carboxyl group-containing compound is a compound having a carboxyl group. Examples of a carboxyl group-containing compound are (poly)acrylic acid, (poly)methacrylic acid, etc.

[0119] Specific examples of ketone group-containing compounds include (poly)diacetone acrylamide and diacetone alcohol. Specific examples of hydrazide compounds include hydrazine, carbohydrazide, and adipic acid hydrazide. Specific examples of melamine compounds include melamine resins and methyl etherified melamine resins.

[0120] [Amount of Curing Agent] The amount of curing agent may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the wax, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0121] [Other Components] The repellent may contain other components in addition to the above components. Examples of other components include polysaccharides, paper strength agents, flocculants, retention aids, coagulants, binder resins, anti-slip agents, sizing agents, paper strength agents, fillers, antistatic agents, preservatives, UV absorbers, antibacterial agents, deodorizers, fragrances, etc. These may be used alone or in combination of two or more. In addition to the above components, other components include other water and / or oil repellents, dispersants, texture adjusters, softeners, flame retardants, paint fixatives, wrinkle inhibitors, drying speed adjusters, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity adjusters, UV absorbers, antioxidants, pH adjusters, insect repellents, antifoaming agents, shrinkage inhibitors, anti-wrinkle agents after washing, shape retention agents, drape retention agents, ironing improvers, whitening agents, whitening agents, fabric softening clay, dye transfer inhibitors such as polyvinylpyrrolidone, polymer dispersants, stain release agents, scum dispersants, fluorescent whitening agents such as 4,4-bis(2-sulfostyryl)biphenyl disodium (Tinopal CBS-X manufactured by Ciba Specialty Chemicals), dye fixatives, and anti-fading agents such as 1,4-bis(3-aminopropyl)piperazine. The following may be blended: stain removers, enzymes such as cellulase, amylase, protease, lipase, keratinase, etc. as fiber surface modifiers; foam inhibitors; silk protein powder, surface-modified products thereof, 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 Soluble S (Ichimaru Falcos)); stain inhibitors (e.g., nonionic polymer compounds composed of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units (e.g., FR627 manufactured by GOO Chemical Industry Co., Ltd.), SRC-1 manufactured by Clariant Japan, etc.) that can impart silk texture and functionality such as moisture absorption and release. These may be used alone or in combination of two or more.

[0122] [Amount of Other Components] The amount of each or the total amount of the other components may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the wax, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0123] <Pulp composition> The pulp composition according to the present disclosure contains pulp and a repellent component. The pulp composition according to the present disclosure is obtained by treating pulp with a repellent.

[0124] [Pulp] The pulp composition contains pulp, and the pulp is treated with a repellent as a pulp base material. The pulp base material may be in the form of pulp alone, pulp slurry, pulp product, etc. Examples of the pulp base material include pulp such as bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulp such as groundwood pulp, mechanical pulp or thermomechanical pulp; pulp slurries containing the above pulp; and pulp products such as paper, paper containers, and molded paper products made from recycled paper pulp such as recycled newspaper, recycled magazine paper, recycled corrugated cardboard, and deinked recycled paper. Specific examples of pulp products include food packaging materials, food containers, gypsum board base paper, coated base paper, medium-quality paper, general liners and corrugating media, neutral pure white roll paper, neutral liners, rust-proof liners and metal interleaving paper, kraft paper, neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper, molded paper (molded containers), etc. Suitable examples of pulp products include food packaging materials and food containers, and particularly pulp molded products for food contact applications.

[0125] The amount of pulp in the pulp composition may be 0.1% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 50% by weight or more, 75% by weight or more, or 90% by weight or more, and may be 99% by weight or less, 75% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, 4% by weight or less, or 3% by weight or less. Typically, when the pulp composition is prepared by internal addition, the amount of pulp in the pulp composition is 30% by weight or less, and when the pulp composition is prepared by external addition, the amount of pulp in the pulp composition may be 75% by weight or more.

[0126] [Liquid Medium] The pulp composition may contain a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent, and is typically an aqueous medium, particularly water. The liquid medium may also contain a liquid medium derived from a repellent agent.

[0127] [Amount of Liquid Medium] The amount of the liquid medium in the pulp composition may be 0.1 wt% or more, 0.5 wt% or more, 1 wt% or more, 3 wt% or more, 5 wt% or more, 10 wt% or more, 20 wt% or more, 30 wt% or more, 50 wt% or more, 75 wt% or more, 90 wt% or more, or 95 wt% or more, and may be 99 wt% or less, 75 wt% or less, 50 wt% or less, 40 wt% or less, 30 wt% or less, 20 wt% or less, 10 wt% or less, 5 wt% or less, 4 wt% or less, or 3 wt% or less. Typically, when the pulp composition is prepared by internal addition, the amount of the liquid medium in the pulp composition is 50 wt% or more, particularly 90 wt% or more, and when the pulp composition is prepared by external addition, the amount of the liquid medium in the pulp composition is 30 wt% or less, particularly 10 wt% or less.

[0128] [Repellent] The pulp composition may contain wax in a repellent, which will be described in detail separately in <Repellent>.

[0129] The amount of repellent added to the pulp base material may be adjusted to a desired 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, and may be 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, preferably 5.0% by weight or less, more preferably 3.0% by weight or less, based on the pulp.

[0130] In the external addition treatment, the amount of wax contained in the coating layer is 0.01 g / m ２ Above, 0.03g / m ２ Above, 0.05g / m ２ Above, 0.1g / m ２ Above, 0.3g / m ２ Above, 0.5g / m ２ or more, or 1.0 g / m ２ or more, and ２ Below, 4.0g / m ２ Below, 3.0g / m ２ Below, 2.0g / m ２ Below, 1.0g / m ２ Below, 0.5g / m ２ Below, 0.3g / m ２ or less, or 0.1 g / m ２ It may be the following:

[0131] [Paper Strength Agent] The pulp composition may contain a paper strength agent. Examples of the paper strength agent include polyacrylamide-based paper strength agents such as cationic polyacrylamide, anionic polyacrylamide, and amphoteric polyacrylamide; polysaccharide-based paper strength agents such as starch, enzyme-modified starch, thermochemically modified starch, oxidized starch, esterified starch, etherified starch (e.g., hydroxyethylated starch), aldehyde-modified starch, cationized starch, starch, xanthan gum, karaya gum, welan gum, guar gum, pectin, tamarind gum, carrageenan, chitosan, gum arabic, locust bean gum, cellulose, alginic acid, agar, dextran, cellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, chitin nanofiber, cellulose nanofiber, and pullulan, and modified polysaccharides thereof (e.g., modified polysaccharides into which a hydroxyl group or a cationic group has been introduced); Polyamide-based paper strength agents such as polyamide resins, polyamine resins, polyamide-polyamine resins, polyamide-epichlorohydrin resins, polyamide-polyamine-epichlorohydrin resins, polyamide-polyurea-formaldehyde resins, and epoxidized polyamide resins; urea / melamine-based paper strength agents such as urea resins, melamine resins, urea-formaldehyde resins, and melamine-formaldehyde resins; polyvinyl alcohol-based paper strength agents such as polyvinyl alcohol, fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, cation-modified polyvinyl alcohol, and terminally alkyl-modified polyvinyl alcohol; styrene-butadiene copolymers, polyvinyl acetate, vinyl chloride-vinyl acetate copolymers, polyvinyl chloride, polyvinylidene chloride, polyacrylic acid esters, fatty acid diamides, polyethyleneimine resins, and ketone aldehyde resins. The paper strength agent in the present disclosure is preferably a polyacrylamide-based paper strength agent, a polysaccharide-based paper strength agent, or a polyamide-based paper strength agent.

[0132] [Amount of Paper Strength Agent] The amount of the paper strength agent may be 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more, and may be 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, and is preferably 5.0% by weight or less, based on the pulp.

[0133] [Sizing Agent] The pulp composition may contain a sizing agent. Examples of the sizing agent include cationic sizing agents, anionic sizing agents, neutral sizing agents, and amphoteric sizing agents, such as rosin-based sizing agents (e.g., acidic rosin-based sizing agents, neutral rosin-based sizing agents), alkyl ketene dimers, and alkenyl succinic anhydrides.

[0134] [Amount of Sizing Agent] The amount of sizing agent may be 0.1% by weight or more, 0.2% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more, and may be 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, based on the pulp.

[0135] [Other Additives] In addition to the above, the pulp composition may contain additives used in the production of pulp products, such as fixing agents (aluminum sulfate, etc.), organic acids (formic acid, acetic acid, etc.), flocculants, retention aids, dyes, fluorescent dyes, slime control agents, defoamers, etc. The pulp composition contains components derived from the repellent, but each of the components that can be contained in the above-mentioned repellent may also be added to the pulp composition as an additive.

[0136] The amount of each of the above additives may be 0.1% by weight or more, 1% by weight or more, 3% by weight or more, or 5% by weight or more, and may be 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, 1% by weight or less, or 0.5% by weight or less, based on the weight of the pulp.

[0137] <Method for producing a pulp product> The method for producing a pulp product according to the present disclosure may include a step of treating a pulp base material with a repellent. The pulp base material is treated with the repellent to obtain a pulp composition. The obtained pulp composition can be subjected to treatment steps such as drying, heating, and molding as necessary to obtain a pulp product.

[0138] The above description of the "pulp composition" is used to refer to the type and composition of the pulp substrate and repellent. The repellent of the present disclosure can be applied to a substrate as a treatment agent (particularly a surface treatment agent) by a conventionally known method. The treatment method may involve dispersing and diluting the repellent of the present disclosure in an organic solvent or water, as necessary, and applying it to the interior and / or surface of the pulp substrate by a known method such as dip coating, spray coating, foam coating, or the like, followed by drying. After drying, a pulp product is obtained to which the solid components of the repellent are attached. If necessary, the repellent may be applied together with an appropriate crosslinking agent and cured. The concentration of the repellent in the treatment agent to be contacted with the pulp substrate may be varied depending on the application, but may be 0.01 to 10% by weight, for example, 0.05 to 5% by weight.

[0139] The repellent agent can be applied to the pulp substrate by any of the known methods for treating a pulp substrate with a liquid. The pulp substrate may be immersed in the repellent agent, the pulp substrate and the repellent agent may be mixed, or the solution may be applied or sprayed onto the pulp substrate. The treated pulp substrate is preferably dried and cured by heating to develop liquid repellency. The heating temperature may be, for example, 100°C to 200°C, 100°C to 170°C, or 100°C to 120°C. In the present disclosure, the heating time may be 5 seconds to 60 minutes, for example, 30 seconds to 3 minutes.

[0140] The pulp base material can be treated by an internal treatment method in which a repellent is added to pulp before papermaking (e.g., pulp slurry), or an external treatment method in which a repellent is applied to pulp after papermaking (e.g., pulp product). Examples of internal treatment methods include mixing, immersion, etc., and may include a step of adding a repellent to pulp slurry and stirring and mixing. Examples of external treatment methods include spraying, application, etc., and specific examples include pond-type two-roll size presses, gate roll-type, and rod metering size presses. The treatment may be an external treatment or an internal treatment. For example, when the pulp base material is paper, the repellent may be coated on the paper, or the solution may be attached or sprayed on the paper, or the repellent may be mixed with the pulp slurry before papermaking.

[0141] The treatment method may be an internal addition treatment in which a repellent is added to the pulp slurry before papermaking. The internal addition treatment may include, but is not limited to, one or more of the following steps: adding a repellent to the pulp slurry and stirring and mixing it; suction-dehydrating the pulp composition prepared in the above step through a mesh of a predetermined shape to deposit the pulp composition and form a molded pulp product intermediate; and molding and drying the molded pulp product intermediate in a heated mold to obtain a molded pulp product. The treated paper may be briefly dried at room temperature or at an elevated temperature, and then optionally subjected to a heat treatment depending on the paper's properties. The heat treatment temperature may be 150°C or higher, 180°C or higher, or 210°C or higher, and may be 300°C or lower, 250°C or lower, or 200°C or lower, and particularly may be 80°C to 180°C. Heat treatment within this temperature range can exhibit excellent oil resistance, water resistance, etc. The internally treated pulp base material may be treated with an external additive to be treated with a repellent, and additional wax and additional paper strength agent may be attached to the surface.

[0142] The treatment method may be an external addition treatment in which a repellent agent is applied to the pulp base material after papermaking. Size presses for external addition treatment can also be divided into the following categories based on the application method. One application method is the so-called pond-type two-roll size press, in which a coating liquid (size liquid) is supplied to the nip formed by passing paper between two rubber rolls, creating a coating liquid pool called a pond, and the paper is passed through this coating liquid pool to apply the size liquid to both sides of the paper. Other application methods include the gate roll type, in which the size liquid is applied using a surface transfer method, and the rod metering size press. In the pond-type two-roll size press, the size liquid easily penetrates into the paper, while in the surface transfer type, the size liquid components tend to remain on the paper surface. In the surface transfer type, the coating layer tends to remain on the paper surface compared to the pond-type two-roll size press, and a larger coating layer is formed on the surface than in the pond-type two-roll size press. In the present disclosure, performance can be imparted to paper even when the former pond-type two-roll size press is used. Papers treated in this way may exhibit excellent oil and water resistance etc., after simple drying at room temperature or at elevated temperatures, optionally followed by a heat treatment which may range in temperature up to 300°C, e.g. up to 200°C, especially 80°C to 180°C, depending on the properties of the paper.

[0143] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to these examples.

[0144] <Test Method> The test procedure is as follows.

[0145] [Volume abundance ratio and median diameter (D50) of particles] For the wax and the aqueous dispersion, the volume abundance ratio of particles of 100 μm or more, the volume abundance ratio of particles of 10 μm or more, and the median diameter (D50) were calculated from the volume-based frequency distribution (volume distribution) obtained by measurement using a laser diffraction / scattering device.

[0146] [Average particle size of particles obtained by removing the liquid medium from the oil-resistant agent] The concentration of an aqueous dispersion of the oil-resistant agent was adjusted to 1 wt %. This aqueous dispersion was cast onto aluminum foil and dried at room temperature for one day to remove the liquid medium, thereby preparing an observation sample. The observation sample was observed with a scanning electron microscope to obtain an observation image and observe the particle size. If the particle shape was spherical, the particle diameter was considered to be the particle size, and if the particle shape was non-spherical, the average value of the longest and shortest diameters was considered to be the particle size. By repeatedly measuring the particle size of all particles present within the field of view, moving the field of view, and measuring the particle size again, particle sizes were measured at 100 or more points, and the average value was used as the average particle size of the particles obtained by removing the liquid medium from the oil-resistant agent.

[0147] [Preparation of Pulp Mold] Pulp mold was formed using an automatic molding machine. A mesh-like body was placed on a metal pulp mold mold with multiple suction holes at the bottom, and a metal tank was placed on top. A mixture of pulp slurry and a water-dispersible oil-proofing agent (pulp composition) was placed in the upper metal tank. The pulp composition was sucked and dehydrated through the pulp mold mold and mesh-like body using a vacuum pump from the side of the pulp mold opposite the side where the mesh-like body was placed, and the solids (pulp, etc.) contained in the pulp composition were deposited on the mesh-like body to obtain a pulp mold intermediate. Next, the obtained pulp mold intermediate was dried from above and below in a metal male-female mold heated to 60 to 250°C under a pressure of 0.05 to 5 MPa. This produced a pulp molded product molded into the shape of a container.

[0148] [Oil resistance test] 100 mL of corn oil at 50°C was poured into a pulp mold, and after leaving it at room temperature for 45 minutes, the corn oil was removed from the pulp mold and the degree of staining of the pulp mold was evaluated. The following evaluation values ​​were set depending on the degree of staining: 5: No staining on the inside. 4: Stained on the inside. No staining on the back. 3: Stained on the inside. Slight staining on the back. 2: Stained on the inside. Staining on the back was less than 50% of the area. 1: Stained on the inside. Staining on the back was 50% or more but less than 100% of the area. 0: Stained on the entire back.

[0149] Example 1 2 g of paraffin wax (melting point 69.8°C), 0.2 g of polyethylene oxide alkyl ether (alkyl carbon number 6 to 16, HLB: 7), and 17.8 g of water were mixed to obtain an aqueous dispersion. This aqueous dispersion was heated to 85°C and then treated with an ultrasonic homogenizer for 20 minutes to obtain an aqueous dispersion-type oil-resistant agent. The obtained aqueous dispersion-type oil-resistant agent exhibited the following properties: Median diameter D50: 0.8 μm Volume ratio of particles of 100 μm or more: 0% Volume ratio of particles of 10 μm or more: 12% Charge density: 20 μeq / g

[0150] A pulp composition was prepared by adding a water-dispersible oil-proofing agent to an aqueous pulp slurry having a concentration of 0.5 wt % so that the ratio of the agent to the pulp was 5 wt % in terms of solid content. The pulp-containing water-dispersible oil-proofing agent was placed in an automatic molding machine to produce a pulp mold. The pulp mold was subjected to an oil resistance test and scored 4 points. The results are shown in Table 1.

[0151] Example 2 2 g of microcrystalline wax (melting point 82.9°C), 0.2 g of polyethylene oxide alkyl ether (alkyl carbon number 6 to 16, HLB: 7), and 17.8 g of water were mixed to obtain an aqueous dispersion. This aqueous dispersion was heated to 95°C and then treated with an ultrasonic homogenizer for 20 minutes to obtain an aqueous dispersion-type oil-resistant agent. The obtained aqueous dispersion-type oil-resistant agent exhibited the following properties: median diameter D50: 0.85 μm, volume fraction of particles of 100 μm or larger: 0%, volume fraction of particles of 10 μm or larger: 18%, and charge density: 15 μeq / g.

[0152] Using the obtained water-dispersible oil-proofing agent, a pulp composition was prepared and a pulp mold was produced in the same manner as in Example 1. The pulp mold was subjected to an oil resistance test and scored 4 points. The results are shown in Table 1.

[0153] Example 3 2 g of paraffin wax (melting point 69.8°C), 0.18 g of benzalkonium chloride, and 17.8 g of water were mixed to obtain an aqueous dispersion. This aqueous dispersion was heated to 85°C and then treated with an ultrasonic homogenizer for 20 minutes to obtain an aqueous dispersion-type oil-resistant agent. The obtained aqueous dispersion-type oil-resistant agent exhibited the following properties: Median diameter D50: 0.75 μm Volume ratio of particles of 100 μm or more: 0% Volume ratio of particles of 10 μm or more: 8% Charge density: 75 μeq / g

[0154] Using the obtained water-dispersible oil-proofing agent, a pulp composition was prepared and a pulp mold was produced in the same manner as in Example 1. The pulp mold was subjected to an oil resistance test and scored 4 points. The results are shown in Table 1.

[0155] [Example 4] Microcrystalline wax (melting point 79°C) was crushed to 1 mm or less in a mortar and then dry-pulverized using a jet mill to obtain a microcrystalline wax powder. The particle size of the microcrystalline wax powder was measured using a laser diffraction / scattering device, and the median diameter D50 was found to be 0.99 μm.

[0156] 2 g of microcrystalline wax powder, 0.2 g of polyethylene oxide alkyl ether (alkyl carbon number 6 to 16, HLB: 7), and 17.8 g of water were mixed to obtain a water-dispersible oil-resistant agent. The obtained water-dispersible oil-resistant agent exhibited the following properties: Median diameter D50: 0.95 μm Volume ratio of particles of 100 μm or more: 0% Volume ratio of particles of 10 μm or more: 25% Charge density: 2 μeq / g

[0157] Using the obtained water-dispersible oil-proofing agent, a pulp composition was prepared and a pulp mold was produced in the same manner as in Example 1. The pulp mold was subjected to an oil resistance test and scored 4 points. The results are shown in Table 1.

[0158] Example 5 2 g of paraffin wax, 0.05 g of cationic starch, 0.04 g of an abietic acid derivative (rosin-based sizing agent), 0.04 g of formic acid, 0.04 g of acetic acid, and 7.83 g of water were mixed, heated to 95°C, and then treated with an ultrasonic homogenizer for 20 minutes to obtain a water-dispersible oil-proofing agent. The obtained water-dispersible oil-proofing agent exhibited the following properties: Median diameter D50: 0.6 μm Volume fraction of particles of 100 μm or larger: 0% Volume fraction of particles of 10 μm or larger: 0.2% Charge density: 14 μeq / g

[0159] Using the obtained water-dispersible oil-proofing agent, a pulp composition was prepared and a pulp mold was produced in the same manner as in Example 1. The pulp mold was subjected to an oil resistance test and scored 4 points. The results are shown in Table 1. The average particle size of the particles obtained by removing the liquid medium from the water-dispersible oil-proofing agent was 0.45 μm.

[0160] Example 6 2 g of paraffin wax, 0.10 g of cationic starch, 0.04 g of an abietic acid derivative (rosin-based sizing agent), 0.02 g of formic acid, 0.02 g of acetic acid, and 7.87 g of water were mixed, heated to 95°C, and then treated with an ultrasonic homogenizer for 20 minutes to obtain a water-dispersible oil-proofing agent. The obtained water-dispersible oil-proofing agent exhibited the following properties: Median diameter D50: 0.22 μm Volume fraction of particles of 100 μm or larger: 0% Volume fraction of particles of 10 μm or larger: 0.1% Charge density: 39 μeq / g

[0161] Using the obtained water-dispersible oil-proofing agent, a pulp composition was prepared and a pulp mold was produced in the same manner as in Example 1. The pulp mold was subjected to an oil resistance test and scored 4 points. The results are shown in Table 1. The average particle size of the particles obtained by removing the liquid medium from the water-dispersible oil-proofing agent was 0.84 μm.

[0162] Example 7 2 g of paraffin wax, 0.1 g of sodium oleate, and 8 g of water were mixed, heated to 95°C, and then treated with an ultrasonic homogenizer for 20 minutes to obtain a water-dispersible oil-proofing agent. The obtained water-dispersible oil-proofing agent exhibited the following properties: Median diameter D50: 0.45 μm Volume ratio of particles of 100 μm or more: 0% Volume ratio of particles of 10 μm or more: 0% Charge density: -143 μeq / g

[0163] Using the obtained water-dispersible oil-proofing agent, a pulp composition was prepared and a pulp mold was produced in the same manner as in Example 1. The pulp mold was subjected to an oil resistance test and scored 4 points. The results are shown in Table 1. The average particle size of the particles obtained by removing the liquid medium from the water-dispersible oil-proofing agent was 0.45 μm.

[0164] Example 8 2 g of paraffin wax, 0.2 g of sodium dodecyl sulfate, and 8 g of water were mixed, heated to 95°C, and then treated with an ultrasonic homogenizer for 20 minutes to obtain a water-dispersible oil-resistant agent. The obtained water-dispersible oil-resistant agent exhibited the following properties: Median diameter D50: 0.8 μm Volume ratio of particles of 100 μm or larger: 0% Volume ratio of particles of 10 μm or larger: 12% Charge density: -351 μeq / g

[0165] Using the resulting aqueous dispersion, a pulp composition was prepared and a pulp mold was produced in the same manner as in Example 1. The pulp mold was subjected to an oil resistance test and scored 4 points. The results are shown in Table 1. The average particle size of the particles obtained by removing the liquid medium from the oil-proofing agent was 0.54 μm.

[0166] Comparative Example 1 2 g of paraffin wax, 0.2 g of polyethylene oxide alkyl ether (alkyl carbon number 6 to 16, HLB: 7), and 17.8 g of water were mixed, heated to 90°C, and then allowed to cool while stirring with a magnetic stirrer, to obtain a water-dispersible oil-proofing agent. The obtained water-dispersible oil-proofing agent exhibited the following properties: Median diameter D50: 88 μm Volume proportion of particles of 100 μm or larger: 35% Volume proportion of particles of 10 μm or larger: 98%

[0167] A pulp composition was prepared using the water-dispersible oil-proofing agent in the same manner as in Example 1, and a pulp mold was produced. The pulp mold was subjected to an oil resistance test and scored 2 points. The results are shown in Table 1.

[0168] [Table 1]

Claims

1. Wax particles used in an oil-proofing agent for pulp, the wax having a volume median diameter (D50) of 0.01 μm or more and 1 μm or less.

2. The wax of claim 1 which is a petroleum wax.

3. The wax according to claim 1 or 2, which is at least one selected from the group consisting of paraffin wax and microcrystalline wax.

4. The wax according to any one of claims 1 to 3, which is for internal addition.

5. The wax according to any one of claims 1 to 4, wherein the wax is at least one selected from the group consisting of paraffin wax and microcrystalline wax, is for internal addition, and has a volume median diameter (D50) of 0.1 μm or more and 1 μm or less.

6. An oil-proofing agent for pulp, comprising the wax according to any one of claims 1 to 5.

7. An oil-proofing agent for pulp which is a water-dispersible composition, comprising a wax and a dispersant, and having a volume median diameter (D50) of 0.01 μm or more and 1 μm or less.

8. The oil-proofing agent for pulp according to claim 7, wherein the particles obtained by removing the liquid medium by natural drying at room temperature have an average particle size of 0.01 μm or more and 1 μm or less, as determined from an image observed under a scanning electron microscope.

9. The oil-proofing agent for pulp according to claim 7 or 8, wherein the wax is a petroleum wax.

10. The oil-proofing agent for pulp according to any one of claims 7 to 9, wherein the wax is at least one selected from the group consisting of paraffin wax and microcrystalline wax.

11. The oil-proofing agent for pulp according to any one of claims 7 to 10, having a charge density of -600 μeq / g or more and 100 μeq / g or less.

12. The oil-proofing agent for pulp according to any one of claims 7 to 11, which contains an organic acid or an inorganic acid.

13. The oil-resistant agent for pulp according to any one of claims 7 to 12, wherein the wax is at least one selected from the group consisting of paraffin wax and microcrystalline wax, the dispersant is at least one selected from the group consisting of nonionic dispersants, anionic dispersants, and cationic dispersants, the pulp additive contains an organic acid, the amount of the dispersant is 1 part by weight or more and 50 parts by weight or less per 100 parts by weight of the wax, the volume median diameter (D50) is 0.1 μm or more and 1 μm or less, the volumetric ratio of particles of 100 μm or more is 20% or less, the volumetric ratio of particles of 10 μm or more is 40% or less, and the charge density is -400 μeq / g or more and 400 μeq / g or less.

14. A method for producing a pulp product, comprising the step of treating a pulp substrate with the oil-proofing agent for pulp according to any one of claims 6 to 13.

15. A pulp product treated with the oil-proofing agent for pulp according to any one of claims 6 to 13.

16. The pulp product of claim 15, which is a molded pulp product for food contact applications.

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