Wax and oilproof agent for pulp

Abstract

To provide a novel wax or an oilproof agent for pulp that can apply oil resistance to a pulp substrate.SOLUTION: Disclosed are: a wax that is a wax particle to be used in an oilproof agent for pulp and has a median size (D50) measured by a laser diffraction scattering method of 0.01 μm or over and 1 μm or under; and an oilproof agent for pulp that is an oilproof agent for pulp as a water dispersion type composition, includes a wax and a dispersant, and has a volume median size (D50) of 0.01 μm or over and 1 μm or under.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] Patent Document 1 discloses a masking tape that uses an aqueous emulsion containing a specific paraffin wax as a release treatment agent, thereby preventing repelling of the coated surface. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2011-116836 A Summary of the Invention [Problem to be solved by the invention]

[0004] Patent Document 1 does not describe or suggest 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. [Means for solving the problem]

[0006] The present disclosure includes the following aspects: [Section 1] 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. [Section 2] Item 1. The wax according to item 1, which is a petroleum wax. [Section 3] Item 3. The wax according to item 1 or 2, which is at least one selected from the group consisting of paraffin wax and microcrystalline wax. [Section 4] Item 4. The wax according to any one of items 1 to 3, which is for internal addition. [Section 5] The wax is at least one selected from the group consisting of paraffin wax and microcrystalline wax, For internal use, 5. The wax according to any one of items 1 to 4, wherein the volume median diameter (D50) is 0.1 μm or more and 1 μm or less. [Section 6] Item 6. An oil-proofing agent for pulp, comprising the wax according to any one of items 1 to 5. [Section 7] An oil-proofing agent for pulp which is a water-dispersible composition, Contains a wax and a dispersant, An oil-proofing agent for pulp having a volume median diameter (D50) of 0.01 μm or more and 1 μm or less. [Section 8] 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 an image observed under a scanning electron microscope. [Section 9] Item 9. The oil-proofing agent for pulp according to Item 7 or 8, wherein the wax is a petroleum wax. [Section 10] Item 10. The oil-proofing agent for pulp according to any one of Items 7 to 9, wherein the wax is at least one selected from the group consisting of paraffin wax and microcrystalline wax. [Section 11] Item 11. The oil-proofing agent for pulp according to any one of items 7 to 10, having a charge density of -600 μeq / g or more and 100 μeq / g or less. [Section 12] Item 12. The oil-proofing agent for pulp according to any one of items 7 to 11, comprising an organic acid or an inorganic acid. [Section 13] 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 a nonionic dispersant, an anionic dispersant, and a cationic dispersant; The pulp additive comprises an organic acid, The amount of the dispersant is 1 part by weight or more and 50 parts by weight or less relative to 100 parts by weight of the wax, The volume median diameter (D50) is 0.1 μm or more and 1 μm or less, The volume ratio of particles having a size of 100 μm or more is 20% or less, The volume ratio of particles 10 μm or larger is 40% or less, Item 13. The oil-proofing agent for pulp according to any one of items 7 to 12, having a charge density of -400 μeq / g or more and 400 μeq / g or less. [Section 14] 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. [Section 15] Item 14. A pulp product treated with the oil-proofing agent for pulp according to any one of items 6 to 13. [Section 16] Item 16. The pulp product according to item 15, which is a pulp molded product for food contact applications. Effect of the Invention

[0007] According to the present disclosure, it is possible to impart oil resistance to a pulp base material. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] <Repellent> 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 resistance agent, an oil resistance agent, a water repellent agent, an oil repellent agent, and / or a stain resistance agent. For example, the repellent agent in the present disclosure can be used as an oil resistance agent or an oil resistance agent for pulp.

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

[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 ratio of particles of 100 μm or more in the repellent of the present disclosure measured by a laser diffraction scattering method may be 0.1% or more, 0.3% or more, 0.5% or more, 1% or more, 1.5% or more, 3% or more, 4% or more, 5% or more, or 10% or more, and may be 50% or less, 30% or less, 20% or less, 15% or less, 10% or less, 5% or less, 3% or less, or 1.5% or less. The method for setting the volumetric ratio of particles of 1 μm or more measured by a laser diffraction scattering method to the above range is not limited, but for example, the particles in the raw material and / or dispersion may be finely divided using a grinder, homogenizer, or the like.

[0012] The volumetric ratio of particles having a size of 10 μm or more in the repellent of the present disclosure measured by the laser diffraction scattering method may be 0.05% or more, 0.1% or more, 0.3% or more, 0.5% or more, 1% or more, 1.5% or more, 3% or more, 4% or more, 5% or more, or 10% or more, and may be 50% or less, 30% or less, 20% or less, 15% or less, 10% or less, 5% or less, 3% or less, or 1.5% or less, and preferably 25% or less, 15% or less, or 10% or less. The method for setting the volumetric ratio of particles having a size of 1 μm or more measured by the laser diffraction scattering method to the above range is not limited, but for example, the particles in the raw material and / or dispersion may be finely divided using a grinder, homogenizer, or the like.

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

[0014] The average particle size obtained from the observation image of a scanning electron microscope of particles obtained by removing the liquid medium by natural drying at room temperature from the repellent (e.g., oil-resistant agent for pulp) which is the water-dispersed composition of the present disclosure may be 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.2 μm or more, 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, or 0.6 μm or more, and may be 10 μm or less, 5 μm or less, 3 μm or less, 1 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, 0.3 μm or less, or 0.2 μm or less, preferably 1 μm or less. To obtain a particle size in the above range, for example, a grinder, a homogenizer, or the like may be used to finely pulverize the particles in the raw material and / or the dispersion. The room temperature is 20°C to 30°C, and 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. It may be q / g or more, -200μeq / g or more, -50μeq / g or more, and may be 5000μeq / g or less, 2500μeq / g or less, 1000μeq / g or less, 750μeq / g or less, 500μeq / g or less, 400μeq / g or less, 350μeq / g or less, 300μeq / g or less, 200μeq / g or less, 100μeq / g or less, or 50μeq / g or less, preferably 1000μeq / g or less, more preferably 500μeq / g or less, for example 300μeq / g or less. In particular, the ionic charge density in the repellent of the present disclosure is preferably -600μeq / g or more and 100μeq / 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 an electric charge repulsion to the dispersion, and improve the stability of the aqueous dispersion. In addition, when the substrate has a positive charge, it can enhance the interaction with the substrate, and improve the oil resistance when the substrate is treated. When the repellent has a negative charge, its ionic charge density can 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 an electric charge repulsion to the dispersion, and improve the stability of the aqueous dispersion. In addition, when the substrate has a negative charge, it can enhance the interaction with the substrate, and improve the oil resistance when the substrate is treated. When the repellent has a positive charge, its ionic charge density can 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 in the repellent of the present disclosure can be measured, for example, by the following method.

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

[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 may 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 (e.g., an alkyl group).

[0024] [Characteristics of wax] Possible properties of the wax are given below.

[0025] The wax may be in a particulate form (powder form). The average particle size of the wax may be 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.2 μm or more, 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, or 0.6 μm or more, and may 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, and is preferably 1 μm or less. The above particle size is a primary particle size. By being within the above range, excellent particle stability and good liquid repellency can be obtained. The average particle size can be measured with a microscope (scanning electron microscope). Specifically, a wax particle sample is observed with a microscope at any magnification. Next, if the particle shape is spherical, the diameter is regarded as the particle size, and if it is non-spherical, the average of the longest and shortest diameters is regarded as the particle size. By measuring the particle size of all particles present within the field of view, then moving the field of view and measuring the particle size again, the particle size is measured at 100 or more points, and the average value is regarded as the average particle size.

[0026] The wax in the present disclosure is preferably a wax particle having a predetermined volume abundance ratio or median diameter (D50) of particles measured by a laser diffraction scattering method. In the present disclosure, the laser diffraction scattering method for the wax was performed in a dry state or in a wet state using a medium (e.g., water) that does not dissolve the wax. In the present disclosure, 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-dispersed 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 ratio of particles of 100 μm or more in the wax of the present disclosure measured by the laser diffraction scattering method may be 0.1% or more, 0.3% or more, 0.5% or more, 1% or more, 1.5% or more, 3% or more, 4% or more, 5% or more, or 10% or more, and may be 50% or less, 30% or less, 20% or less, 15% or less, 10% or less, 5% or less, 3% or less, or 1.5% or less, and preferably 25% or less, 15% or less, or 10% or less. The method for setting the volumetric ratio of particles of 1 μm or more measured by the laser diffraction scattering method to the above range is not limited, but for example, the particles in the raw material and / or dispersion may be finely divided using a grinder, homogenizer, or the like.

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

[0029] The volume median diameter of the wax of the present disclosure measured by the 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, 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, and is preferably 1 μm or less. In the present disclosure, the volume median diameter refers to the median diameter (D50) in the volume-based particle size distribution measured by the 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, the substrate can be imparted with good liquid repellency (especially oil repellency). The HD contact angle is the static contact angle of the wax with respect to the spin-coated film, and is obtained by dropping 2 μL of HD on the spin-coated film and measuring the contact angle 1 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 the 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., molecular weight of 1000 or less, or 500 or less) or a polymer. When the wax is a polymer, the weight average molecular weight may be 1000 or more, 3000 or more, 5000 or more, 7500 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more, or may be 10000000 or less, 75000000 or less, 5000000 or less, 3000000 or less, 1000000 or less, 750000 or less, 5000000 or less, 300000 or less, 100000 or less, 750000 or less, 500000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 3 ... or 3000 or less.

[0033] The melting point of the wax may be 30° C. or more, 40° C. or more, 60° C. or more, 80° C. or more, 100° C. or more, or 120° C. or more, preferably 40° C. or more, 50° C. or more, 60° C. or more, 70° C. or more, or 80° C. or more, and may be 250° C. or less, 225° C. or less, 200° C. or less, 150° C. or less, 130° C. or less, 120° C. or less, 110° C. or less, 100° C. or less, 80° C. or less, or 50° C. or less, for example, 150° C. or less, or 100° C. or less. 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 the substrate.

[0035] The wax may be a hydrocarbon compound, or 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 be a hydrocarbon compound or a compound having a hydrocarbon group (e.g., an alkyl group) having 6 to 40 carbon atoms.

[0036] (Optionally substituted monovalent hydrocarbon group) The wax may have a monovalent hydrocarbon group which may have a substituent.

[0037] The hydrocarbon group may be a monovalent hydrocarbon group having 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, and is 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, and is 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', -N(R')2, -COOR', and halogen atoms (wherein R' 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 at each occurrence). The substituent may or may not have active hydrogen. The number of the 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 hydrocarbon group having a substituent, 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 (eg, 1) -OR' (particularly -OH) as a substituent (eg, other than at a terminal position).

[0040] (monovalent polysiloxane group) The wax may contain monovalent polysiloxane groups. The (monovalent) polysiloxane groups as well as the (monovalent) hydrocarbon groups may impart liquid repellency to the substrate.

[0041] The polysiloxane group has the formula: -[-Si(R s )2-O-] a - [In the formula, R s is independently in each occurrence a hydrocarbon group or a reactive group having 1 to 40 carbon atoms; a is an integer between 5 and 10,000. It may be expressed as:

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

[0043] Examples of the hydrocarbon group 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., hydroxyl, amino, mercapto, epoxy, carboxyl, halogen-substituted alkyl, vinyl, (meth)acrylic, (meth)acryloyloxy, and (meth)acrylamide groups, hydrogen atoms directly bonded to silicon atoms, etc.). These functional groups may be directly bonded to silicon atoms, or may be bonded to organic groups directly bonded to silicon atoms. The organic groups may be hydrocarbon groups, such as alkylene groups or divalent aromatic groups. The hydrocarbon groups may have 2 to 12 carbon atoms, and alkylene groups preferably have 2 to 10 carbon atoms. Divalent aromatic groups preferably have 6 to 12 carbon atoms. The reactive groups may be groups selected from the group consisting of hydroxyl, epoxy rings, carboxyl, (meth)acrylic, and amino groups, and may be at least one selected from the group consisting of epoxy rings, hydroxyl, (meth)acrylic, and carboxyl groups.

[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 With respect to the total of R, 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. For example, R s Based on the total number of groups, 50 mol % or more may be methyl or ethyl groups (particularly methyl groups).

[0049] In the polysiloxane group, R is a hydrocarbon group having 6 to 40 carbon atoms. sThe amount of R s 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 the above.

[0050] In the polysiloxane group, R s The amount of R s and 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. 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 -OL s1 -[-Si(R s )2-O-] a -R s -L s1 -[-Si(R s )2-O-] a -Si(R s )3 -L s1 -OL 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, s has one or more reactive groups, R s 50 mol % or more of the total groups are methyl groups, L s1 is a hydrocarbon group having 1 to 20 carbon atoms, a is between 5 and 10,000. JPEG2025038871000001.jpg2169 [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.] etc.

[0055] [Wax example] 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 polymers, silicone wax, etc.), and the like. Petroleum waxes such as paraffin wax, microcrystalline wax, montan wax, ozokerite wax, ceresin wax, and petrolatum wax; Examples of the wax include 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 include 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 separately, or an organic dispersant and an inorganic dispersant may be used in combination.

[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 mean a surfactant.

[0062] The dispersant may be fluorine-free.

[0063] [Nonionic dispersant] The dispersant may include a nonionic dispersant. The nonionic dispersant may be a nonionic surfactant.

[0064] The nonionic dispersant may be a low molecular weight or a high molecular weight dispersant. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may 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 monohydric to tridehydric (particularly dihydric to decahydric) alcohol (e.g., an 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 the 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 the alcohol is a monohydric to tridecahydric (particularly dihydric to decahydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 3 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.

[0069] An example of an alkanolamide is formed from a fatty acid and an alkanolamine. The alkanolamide may be a monoalkanolamide or a dialkanolamine. 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. The alkanolamine may be an alkanol having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, 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 (eg, 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, and the like. Among these, those in which the structure of the alkylene oxide adduct portion and the polyalkylene glycol portion is polyoxyethylene (POE) or polyoxypropylene (POP) or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred. Additionally, the nonionic dispersant need not contain aromatic groups.

[0074] The nonionic dispersant has the formula: R 1 O-(CH2CH2O) p -(R 2 O) q -R 3 [In the formula, R 1 is an alkyl group having 1 to 22 carbon atoms or an alkenyl group or acyl group having 2 to 22 carbon atoms, R 2 each is independently the same or different and is an alkylene group having 3 or more carbon atoms (e.g., 3 to 10), R 3 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms, p is a number equal to or greater than 2, q is a number equal to or greater than 0. The compound may be represented by the formula:

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

[0076] Examples of nonionic dispersants include ethylene oxide and hexylphenol, isooctatylphenol, hexadecanol, oleic acid, alkanes (C 12 -C 16 ) Thiol, Sorbitan Mono Fatty Acid (C7-C 19 ) or alkyl(C 12 -C 18 ) 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 ethoxylates, etc.

[0077] The proportion of the polyoxyethylene block may be 5 to 80% by weight, for example 30 to 75% by weight, particularly 40 to 70% by weight, based on the molecular weight of the nonionic dispersant (copolymer). The average molecular weight of the nonionic dispersant is generally 300 to 5,000, for example, 500 to 3,000. The nonionic dispersant may be a single type, or a mixture of two or more types. The nonionic dispersant may be a mixture of a compound having an HLB (hydrophilic-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 dispersants] The dispersant may include 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., molecular weight of 2000 or less, particularly 10000 or less) or a polymer type (e.g., molecular weight of 2000 or more). The molecular weight of the cationic dispersant may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may be 1000000 or less, 750000 or less, 500000 or less, 250000 or less, 100000 or less, 50000 or less, 10000 or less, 7500 or less, 5000 or less, 25000 or less, 750 or less, or 250 or less.

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

[0081] Low molecular weight cationic dispersants are R 21 -N + (-R 22 )(-R 23 )(-R 24 )X - [In the formula, R 21 , R 22 , R 23 and R 24 is hydrogen or a hydrocarbon group having 1 to 40 carbon atoms, X is an anionic group. R 21 , R 22 , R 23 and R 24 Specific 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: R 1 p -N +R 2 q X - [In the formula, R 1 is C12 or higher (e.g. C 12 ~C 50 ) linear and / or branched aliphatic (saturated and / or unsaturated) groups, R 2 is H, a C1-4 alkyl group, a benzyl group, or a polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (particularly 2, particularly 3) to 50) (CH3 and C2H5 are particularly preferred), X is a halogen atom (e.g., chlorine), or a C1-C4 fatty acid salt, or a C1-C4 sulfonic acid salt; p is 1 or 2, q is 2 or 3, and p+q=4. R 1 may have 12 to 50 carbon atoms, for example, 12 to 30 carbon atoms.

[0083] 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 starch, cationic cellulose (e.g., O-(2-hydroxy-3-(trimethylammonio)propyl hydroxyethyl cellulose chloride), cationic guar gum, cationic xanthan gum, chitosan, and other cationic natural products (particularly cationic sugars); aziridine, vinylimidazole, aminoalkyl methacrylate, N,N,N',N'-tetramethyl-2-butene-1,4-diamine, quaternary dimethylammonium ethyl methacrylic acid, diallyldimethylammonium chloride, dimethylaminopropylamine, quaternary vinylimidazole, and other cationic group-containing monomer polymers.

[0085] [Anionic dispersants] The dispersant may comprise an anionic dispersant. The anionic dispersant may be an anionic surfactant. The dispersant may be free of an anionic dispersant.

[0086] The anionic dispersant may be a low molecular weight or a high molecular weight. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may 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.

[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, phosphoric acid mono- or diester type dispersants, and sulfosuccinates. Examples of anionic dispersants include carboxylates (e.g., fatty acid salts).

[0088] [Amphoteric dispersant] The dispersant may comprise 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. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may 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.

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

[0091] [Inorganic dispersant] The dispersant may comprise 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 a hydrophilic particle.

[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 the dispersant may be, relative to 100 parts by weight of the wax, 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, 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 of the present disclosure may include a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The repellent may be a dispersion or a solution. The repellent of the present disclosure may include at least water.

[0096] Examples of the organic solvent include esters (e.g., esters having 2 to 40 carbon atoms, specifically, ethyl acetate, butyl acetate), ketones (e.g., ketones having 2 to 40 carbon atoms, specifically, methyl ethyl ketone, diisobutyl ketone), alcohols (e.g., alcohols having 1 to 40 carbon atoms, specifically, isopropyl alcohol), aromatic solvents (e.g., toluene and xylene), and petroleum solvents (e.g., alkanes having 5 to 10 carbon atoms, specifically, naphtha, kerosene). The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent may contain a compound having at least one hydroxyl 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 of two or more.

[0097] [Amount of liquid medium] The amount of the liquid medium may be, relative to 1 part by weight of the wax, 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.

[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, based on 1 part by weight of wax.

[0099] The amount of the organic solvent may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, 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 the wax.

[0100] 〔silicone〕 The repellent in 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 1000 or more, 10000 or more, or 50000 or more. The weight average molecular weight of the silicone may be 500000 or less, 2500000 or less, 100000 or less, or 50000 or less.

[0103] [Amount of silicone] The amount of silicone may be, relative to 100 parts by weight of wax, 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.

[0104] [Organic acid] The repellent of the present disclosure may contain an organic acid. As the organic acid, a known one can be used. Examples of the organic acid include carboxylic acid, sulfonic acid, sulfinic acid, etc., and particularly carboxylic acid is preferred. Examples of the carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid, etc., and particularly formic acid or acetic acid is preferred. In the present disclosure, the organic acid may be used alone or in combination of two or more. For example, formic acid and acetic acid may be used in combination. The stability of the aqueous dispersion can be improved by adding an organic acid.

[0105] [Amount of organic acid] The amount of the 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, 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 the wax. The amount of the 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. As the inorganic acid, a known one may be used. Examples of the inorganic acid include hydrogen chloride, hydrogen bromide, hydrogen iodide, nitric acid, boric acid, sulfuric acid, and phosphoric acid. In the present disclosure, the inorganic acid may be used alone or in combination of two or more kinds. The stability of the aqueous dispersion can be improved by adding an inorganic acid.

[0107] [Amount of inorganic acid] The amount of the 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 the wax. The amount of the 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 include a curing agent (an active hydrogen reactive compound or an active hydrogen containing compound).

[0109] The curing agent (crosslinking agent) in the repellent can cure the repellent 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 the active hydrogen reactive compound are isocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds, and hydrazide compounds. Examples of the active hydrogen-containing compound 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 include 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 acts as a crosslinking agent. Examples of the polyisocyanate compound include aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates. The isocyanate compound may be a blocked isocyanate compound (e.g., a blocked polyisocyanate compound). The blocked isocyanate compound is a compound in which the isocyanate group of the isocyanate compound is masked with a blocking agent to suppress the reaction.

[0111] Examples of aliphatic polyisocyanates are 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-di ... 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, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane, etc. 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 the araliphatic polyisocyanate are araliphatic diisocyanate and araliphatic triisocyanate.Specific examples of the araliphatic polyisocyanate are 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 are aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates are 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, uretdione, uretoimine, isocyanurates, iminooxadiazinedione, etc. 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 the polyisocyanate compound is blocked with a blocking agent. It is preferable to use a blocked polyisocyanate compound because it is relatively stable even in a 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, for example, 130°C or higher, the isocyanate group is regenerated and can easily react with the hydroxyl group. Examples of the blocking agent include phenol-based compounds, lactam-based compounds, aliphatic alcohol-based compounds, and oxime-based compounds. The polyisocyanate compounds can be used alone or in combination of two or more kinds.

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

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

[0120] [Amount of hardener] The amount of the curing agent may be, relative to 100 parts by weight of the wax, 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.

[0121] [Other ingredients] The repellent may contain other components in addition to the above components. Examples of the other components include polysaccharides, paper strength agents, flocculants, retention aids, coagulants, binder resins, slip prevention agents, sizing agents, paper strength agents, fillers, antistatic agents, preservatives, ultraviolet absorbers, antibacterial agents, deodorants, fragrances, etc. These may be used alone or in combination of two or more. In addition to the above-mentioned components, other components include other water and / or oil repellents, dispersants, texture adjusters, softeners, flame retardants, paint fixing agents, anti-wrinkle agents, drying speed adjusters, crosslinking agents, film-forming agents, compatibilizers, antifreeze agents, viscosity adjusters, UV absorbers, antioxidants, pH adjusters, insect repellents, defoamers, shrink prevention agents, laundry wrinkle prevention agents, shape retention agents, drape retention agents, ironing improvers, whitening agents, whitening agents, fabric softening clay, dye transfer inhibitors such as polyvinylpyrrolidone, polymer dispersants, dirt removers, scum dispersants, fluorescent whitening agents such as 4,4-bis(2-sulfostyryl)biphenyl disodium (Ciba Specialty Chemicals' Chinopearl CBS-X), dye fixatives, and discoloration inhibitors such as 1,4-bis(3-aminopropyl)piperazine. The following can be blended: stain removers, enzymes such as cellulase, amylase, protease, lipase, keratinase, etc. as fiber surface modifiers, foam inhibitors, silk protein powders, their surface modified products or emulsified dispersions (e.g., K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemicals), hydrolyzed silk liquid (Jomo), Silkgen G Soluble S (Ichimaru Falcos)), stain prevention agents (e.g., nonionic polymer compounds consisting 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.), etc. These may be used alone or in combination of two or more.

[0122] [Amount of other ingredients] The amount or total amount of the other components may be, relative to 100 parts by weight of the wax, 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.

[0123] <Pulp composition> The pulp composition according to the present disclosure includes 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 slurry containing the above pulp, and pulp products such as paper, paper containers, and paper molded bodies made of waste paper pulp such as recycled newspaper, recycled magazine, recycled 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 cores, 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 heat-sensitive 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 in particular 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 comprise a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent, typically an aqueous medium, especially water. The liquid medium may comprise 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% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 50% by weight or more, 75% by weight or more, 90% by weight or more, or 95% by weight or more, 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 the liquid medium in the pulp composition is 50% by weight or more, particularly 90% by weight or more, and when the pulp composition is prepared by external addition, the amount of the liquid medium in the pulp composition is 30% by weight or less, particularly 10% by weight or less.

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

[0129] [Amount of repellent] The amount of the repellent added to the pulp substrate may be adjusted so that the wax is in a desired amount. The amount of the 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 additive treatment, the amount of wax contained in the coating layer is 0.01 g / m 2 More than 0.03g / m 2 More than 0.05g / m 2 More than 0.1g / m 2 More than 0.3g / m 2 More than 0.5g / m 2 or more, or 1.0 g / m 2 or more, and 5.0 g / m 2 Below 4.0g / m 2 Below 3.0g / m 2 Below 2.0g / m 2 Below 1.0g / m 2 Below 0.5g / m 2 Below 0.3g / m 2 or less than 0.1 g / m 2 It may be the following:

[0131] [Paper strength agent] The pulp composition may include a strength agent. Examples of strength agents 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, etc.), aldehyde 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 having hydroxyl groups or cationic groups introduced therein); 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 resin, melamine resin, urea-formaldehyde resin, and melamine-formaldehyde resin; 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 terminal alkyl-modified polyvinyl alcohol; Examples of the paper strength agent include styrene-butadiene copolymer, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, polyacrylic acid ester, fatty acid diamide, polyethyleneimine resin, ketone aldehyde resin, etc. As the paper strength agent in the present disclosure, polyacrylamide-based paper strength agents, polysaccharide-based paper strength agents, or polyamide-based paper strength agents are preferable.

[0132] [Amount of paper strength agent] The amount of the 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.

[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 the sizing agent may be 0.1% by weight or more, 0.2% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more, 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 manufacture 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 may be contained in the repellent described above may 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, 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] <Manufacturing method of pulp products> 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 a treatment step such as drying, heating, molding, etc., as necessary, to obtain a pulp product.

[0138] The above description of the "pulp composition" is used for the type and composition of the pulp base material and the repellent. The repellent of the present disclosure can be applied to the base material as a treatment agent (particularly a surface treatment agent) by a conventionally known method. The treatment method may be a method in which the repellent of the present disclosure is dispersed and diluted in an organic solvent or water as necessary, and is attached to the inside and / or surface of the pulp base material by a known method such as dip coating, spray coating, foam coating, etc., and then dried. After drying, a pulp product is obtained to which the solid components of the repellent are attached. If necessary, it may be applied together with a suitable crosslinking agent and cured. The concentration of the repellent in the treatment agent to be contacted with the pulp base material may be appropriately changed depending on the application, but may be 0.01 to 10% by weight, for example, 0.05 to 5% by weight.

[0139] The repellent can be applied to the pulp substrate by any of the methods known for treating the pulp substrate with a liquid. The pulp substrate may be immersed in the repellent, the pulp substrate and the repellent 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] As a method for treating the pulp base material, an internal addition treatment method in which a repellent is added to the pulp (e.g., pulp slurry) before papermaking, or an external addition treatment method in which a repellent is applied to the pulp (e.g., pulp product) after papermaking can be used. Examples of the internal addition treatment method include mixing, immersion, etc., and may include a step of adding a repellent to the pulp slurry and stirring and mixing. Examples of the external addition treatment method include spraying, coating, etc., and specifically include a pond type two-roll size press, a gate roll type, and a rod metering size press. The treatment may be an external addition treatment or an internal addition treatment. For example, when the pulp base material is paper, the paper may be coated with the repellent, or the solution may be attached or sprayed onto the paper, or the paper may be mixed with the pulp slurry before papermaking and treated.

[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: a step of adding a repellent to the pulp slurry and stirring and mixing it; a step of suction-dehydrating the pulp composition prepared in the step through a mesh body of a predetermined shape to deposit the pulp composition to form a pulp molded intermediate; and a step of molding and drying the pulp molded intermediate using a heated mold to obtain a pulp molded product. The treated paper may be subjected to a heat treatment depending on the properties of the paper after simple drying at room temperature or at a high temperature. The temperature of the heat treatment may be 150°C or higher, 180°C or higher, or 210°C or higher, and may be 300°C or lower, 250°C or lower, or 200°C or lower, and may be particularly 80°C to 180°C. By performing the heat treatment in such a temperature range, excellent oil resistance and water resistance can be exhibited. The pulp base material that has been internally treated may be treated with an external additive to treat it with a repellent, and further wax and further paper strength agent may be attached to the surface.

[0142] The treatment method may be an external addition treatment in which a repellent is applied to the pulp base material after papermaking. The size press for external addition treatment can also be divided as follows according to the application method. One application method is a so-called pond type two-roll size press in which a coating liquid (sizing liquid) is supplied to a nip formed by passing paper between two rubber rolls, a coating liquid pool called a pond is created, and the paper is passed through this coating liquid pool to apply the sizing liquid to both sides of the paper. Other application methods are a gate roll type in which the sizing liquid is applied by a surface transfer type, and a rod metering size press. In the pond type two-roll size press, the sizing liquid is likely to penetrate into the inside of the paper, and in the surface transfer type, the sizing liquid components are likely to remain on the surface of the paper. In the surface transfer type, the coating layer is more likely to remain on the surface of the paper than in the pond type two-roll size press, and the coating layer formed on the surface is larger than in the pond type two-roll size press. In the present disclosure, performance can be imparted to the paper even when the former pond type two-roll size press is used. Papers thus treated may exhibit excellent oil and water resistance etc., optionally followed by a heat treatment which, depending on the nature of the paper, may range from 80°C to 180°C, for example up to 300°C, for example up to 200°C, after simple drying at room or elevated temperature. EXAMPLES

[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 ratio and median diameter (D50) of particles] For the wax and water dispersion, the volumetric abundance ratio of particles of 100 μm or more, the volumetric 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 the oil-resistant agent's aqueous dispersion 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 to prepare 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 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 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, the particle size was measured at more than 100 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] [Making pulp molds] Pulp mold was formed using an automatic molding machine. A mesh-like body was placed on a metal pulp mold mold with many suction holes at the bottom, and a metal tank was placed at the top, with a mixture of pulp slurry and water-dispersed oil-proofing agent (pulp composition) being placed in the upper metal tank. The pulp composition was sucked and dehydrated through the pulp mold mold and mesh-like body by a vacuum pump from the side opposite to the side where the mesh-like body was placed in the pulp mold mold, and the solid content (pulp, etc.) contained in the pulp composition was deposited on the mesh-like body to obtain a pulp mold intermediate. Next, the obtained pulp mold intermediate was dried under a pressure of 0.05 to 5 MPa from above and below in a male-female metal mold heated to 60 to 250°C. In this way, a pulp molded product molded into a container shape was produced.

[0148] [Oil resistance test] 100 mL of corn oil at 50°C was poured into the pulp mold, and after leaving it at room temperature for 45 minutes, the corn oil was removed from the pulp mold and the degree of soaking into the pulp mold was evaluated. The following evaluation values ​​were set according to the degree of soaking. 5: No stains on the inside. 4: Stain on the inside. No stain on the back. 3: Stain on the inside. Slight seepage on the back. 2: Stain on the inside. Less than 50% of the area has seeped through to the back. 1: Stain on the inside. Stain on the back is 50% or more but less than 100% of the area. 0: Seeping through to the entire back side.

[0149] [Example 1] 2g of paraffin wax (melting point 69.8°C), 0.2g of polyethylene oxide alkyl ether (alkyl carbon number 6-16 HLB: 7), and 17.8g 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 showed the following properties. Median diameter D50: 0.8 μm Volume ratio of particles over 100 μm: 0% Volume ratio of particles 10 μm or larger: 12% Charge density: 20 μeq / g

[0150] A water-dispersible oil-proofing agent was added to an aqueous pulp slurry having a concentration of 0.5 wt% so that the ratio of the water-dispersible oil-proofing agent to the pulp was 5 wt% in terms of solid content, to prepare a pulp composition. The pulp-containing water-dispersible oil-proofing agent was put into an automatic molding machine to prepare a pulp mold. When the pulp mold was subjected to an oil resistance test, it received a score of 4. The results are shown in Table 1.

[0151] [Example 2] 2g of microcrystalline wax (melting point 82.9°C), 0.2g of polyethylene oxide alkyl ether (alkyl carbon number 6-16 HLB: 7), and 17.8g 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 showed the following properties. Median diameter D50: 0.85 μm Volume ratio of particles over 100 μm: 0% Volume ratio of particles 10 μm or larger: 18% Charge density: 15 μeq / g.

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

[0153] [Example 3] 2g of paraffin wax (melting point 69.8°C), 0.18g of benzalkonium chloride, and 17.8g 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 showed the following properties. Median diameter D50: 0.75 μm Volume ratio of particles over 100 μm: 0% Volume ratio of particles 10 μm or larger: 8% Charge density: 75 μeq / g

[0154] Using the obtained water-dispersible oil-proofing agent, a pulp composition was prepared in the same manner as in Example 1, and a pulp mold was produced. When the pulp mold was subjected to an oil resistance test, it received a score of 4. 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 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 0.99 μm.

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

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

[0158] [Example 5] 2g of paraffin wax, 0.05g of cationic starch, 0.04g of abietic acid derivative (rosin-based sizing agent), 0.04g of formic acid, 0.04g of acetic acid, and 7.83g of water were mixed, heated to 95°C, and treated with an ultrasonic homogenizer for 20 minutes to obtain a water-dispersible oil-resistant agent. The obtained water-dispersible oil-resistant agent showed the following properties. Median diameter D50: 0.6 μm Volume ratio of particles over 100 μm: 0% Volume ratio of particles 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 in the same manner as in Example 1, and a pulp mold was produced. When the pulp mold was subjected to an oil resistance test, it received a score of 4. The results are shown in Table 1. The average particle size of the particles obtained by removing the liquid medium from the water-dispersed oil-proofing agent was 0.45 μm.

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

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

[0162] [Example 7] 2g of paraffin wax, 0.1g of sodium oleate, and 8g of water were mixed, heated to 95℃, 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 showed the following properties. Median diameter D50: 0.45 μm Volume ratio of particles over 100 μm: 0% Volume ratio of particles 10 μm or larger: 0% Charge density: -143 μeq / g

[0163] Using the obtained water-dispersible oil-proofing agent, a pulp composition was prepared in the same manner as in Example 1, and a pulp mold was produced. When the pulp mold was subjected to an oil resistance test, it received a score of 4. The results are shown in Table 1. The average particle size of the particles obtained by removing the liquid medium from the water-dispersed 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 over 100 μm: 0% Volume ratio of particles 10 μm or larger: 12% Charge density: -351 μeq / g

[0165] Using the obtained aqueous dispersion, a pulp composition was prepared in the same manner as in Example 1, and a pulp mold was produced. When the pulp mold was subjected to an oil resistance test, it received a score of 4. 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] 2g of paraffin wax, 0.2g of polyethylene oxide alkyl ether (alkyl carbon number 6-16 HLB: 7), and 17.8g of water were mixed and heated to 90℃, and then cooled while stirring with a magnetic stirrer to obtain a water-dispersible oil-resistant agent. The obtained water-dispersible oil-resistant agent showed the following properties. Median diameter D50: 88 μm Volume ratio of particles 100 μm or larger: 35% Volume ratio of particles 10 μm or larger: 98%

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

[0168] [Table 1] TIFF2025038871000002.tif67164

Claims

1. A wax particle 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. 10. The wax of claim 1 which is a petroleum wax.

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

4. The wax according to claim 1, which is for internal addition.

5. The wax is at least one selected from the group consisting of paraffin wax and microcrystalline wax, For internal use, The wax according to claim 1, wherein the volume median diameter (D50) is 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, Contains a wax and a dispersant, An oil-proofing agent for pulp, having a volume median diameter (D50) of 0.01 μm or more and 1 μm or less.

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

10. 8. The oil-proofing agent for pulp according to claim 7, 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 claim 7, 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 claim 7, which comprises an organic acid or an inorganic acid.

13. 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 a nonionic dispersant, an anionic dispersant, and a cationic dispersant; The pulp additive comprises an organic acid, The amount of the dispersant is 1 part by weight or more and 50 parts by weight or less relative to 100 parts by weight of the wax, The volume median diameter (D50) is 0.1 μm or more and 1 μm or less, The volume ratio of particles having a size of 100 μm or more is 20% or less, The volume ratio of particles having a size of 10 μm or more is 40% or less, The oil-proofing agent for pulp according to claim 7, having a charge density of -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 7 to 13.

15. A pulp product treated with the oil-proofing agent for pulp according to any one of claims 7 to 13.

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

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