Oil resistant agent for waxes and pulp

Abstract

The present invention provides: a novel wax for use in an oil-resistant agent for paper pulp, the wax being wax particles having a median diameter (D50) of 0.01-1 [mu] m as measured by laser diffraction scattering, the oil-resistant agent for paper pulp being a water-dispersed composition, containing a wax and a dispersant, having a volume median diameter (D50) of 0.01-1 [mu] m, and having a median diameter (D50) of 0.01-1 [mu] m as measured by the laser diffraction scattering method; with this oil-resistant agent for pulp, it is possible to impart oil resistance to a pulp base material.

Description

TECHNICAL FIELD

[0001] The present application relates to a wax and a pulp oil repellent. BACKGROUND

[0002] Patent Literature 1 discloses a masking tape in which repulsion of a coated surface does not occur by using an aqueous emulsion containing a specific paraffin wax as a release treatment agent.

[0003] PRIOR ART DOCUMENTS PATENT LITERATURE Patent Literature 1: Japanese Patent Application Laid-Open No. 2011-116836 SUMMARY

[0004] PROBLEMS TO BE SOLVED BY THE INVENTION In Patent Literature 1, there is neither description nor suggestion that a specific particle diameter of wax is used for a pulp use, and there is neither description nor suggestion of the performance of oil repellency.

[0005] An object of the present application is to provide a novel wax or a pulp oil repellent capable of imparting oil repellency to a pulp base material.

[0006] MEANS FOR SOLVING THE PROBLEMS The present application includes the following modes: [Item 1] A wax is a wax particle for a pulp oil repellent, and the volume median diameter (D50) of the wax is 0.01 μm or more and 1 μm or less.

[0007] [Item 2] The wax according to Item 1 is a petroleum wax.

[0008] [Item 3] The wax according to Item 1 or 2 is at least one selected from the group consisting of paraffin wax and microcrystalline wax.

[0009] [Item 4] The wax according to any one of Items 1 to 3 is used for internal addition.

[0010] [Item 5] The wax according to any one of Items 1 to 4, wherein the wax is at least one selected from the group consisting of paraffin wax and microcrystalline wax, the wax is used for internal addition, and the volume median diameter (D50) is 0.1 μm or more and 1 μm or less.

[0011] [Item 6] A pulp oil repellent containing the wax according to any one of Items 1 to 5.

[0012] [Item 7] An oil-resistant agent for pulp is a water-dispersible composition comprising a wax and a dispersant, wherein the volume median particle size (D50) of the oil-resistant agent for pulp is 0.01 μm or more and 1 μm or less.

[0013] [Item 8] The oil-resistant agent for pulp as described in item 7, wherein the average particle size of the particles obtained by removing the liquid medium through natural drying at room temperature, as observed by a scanning electron microscope, is 0.01 μm to 1 μm.

[0014] [Item 9] Oil-resistant agent for pulp as described in item 7 or 8, wherein the wax is a petroleum wax.

[0015] [Item 10] Oil-resistant agent for pulp as described in any one of items 7 to 9, wherein the wax is at least one selected from paraffin wax and microcrystalline wax.

[0016] [Item 11] The oil-resistant agent for pulp as described in any one of items 7 to 10 has a charge density of -600 μeq / g or more and 100 μeq / g or less.

[0017] [Item 12] The oil-resistant agent for pulp as described in any one of items 7 to 11 contains an organic acid or an inorganic acid.

[0018] [Item 13] The oil-resistant agent for pulp as described in any one of items 7 to 12, wherein... The wax mentioned above is selected from at least one of paraffin wax and microcrystalline wax. The dispersant mentioned above is at least one selected from nonionic dispersants, anionic dispersants, and cationic dispersants. The aforementioned pulp additives contain organic acids. The amount of the dispersant is 1 part by weight or less and 50 parts by weight relative to 100 parts by weight of the wax mentioned above. The above-mentioned volumetric median particle size (D50) is between 0.1 μm and 1 μm. The volume fraction of particles larger than 100 μm is less than 20%. The volume fraction of particles larger than 10 μm is less than 40%. The charge density is between -400 μeq / g and 400 μeq / g.

[0019] [Item 14] A method for manufacturing pulp products, comprising the step of treating a pulp substrate with any of the oil-resistant agents for pulp described in any one of claims 6 to 13.

[0020] [Item 15] A pulp product obtained by treating the pulp with the oil-resistant agent described in any one of items 6 to 13.

[0021] [Item 16] The pulp product described in item 15, which is a pulp molded product for food contact use.

[0022] Effects of the Invention According to the present invention, it is possible to impart oil resistance to a pulp substrate. DETAILED DESCRIPTION

[0023] <Agent> The agent of the present invention adheres to a substrate (particularly, a pulp substrate), and is capable of imparting liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or stain resistance, to the substrate, and also functions as a water-resistant agent, an oil-resistant agent, a water-repellent agent, an oil-repellent agent, and / or a stain-resistant agent. For example, the agent of the present invention can be used as an oil-resistant agent, a pulp oil-resistant agent.

[0024] The agent of the present invention can contain a wax as an effective component (as for the wax, further detailed description is given in the item of "Wax"). The wax itself can be used as the agent, or can be used in combination with other components described below as the agent.

[0025] The agent of the present invention can not include any 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 agent of the present invention is capable of imparting liquid repellency to a substrate even if it does not contain these fluorine compounds.

[0026] The volume presence ratio of particles of 100 μm or more in the agent of the present invention measured by the laser diffraction scattering method can 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 can 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 of making the volume presence ratio of particles of 1 μm or more in the range described above is not limited, and, for example, it is possible to make the particles in the raw material and / or dispersion liquid fine by using a pulverizer or a homogenizer, or the like.

[0027] The volume ratio of particles of 10 μm or more in the application's sizing agent, as measured by laser diffraction scattering, can 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 can be 50% or less, 30% or less, 20% or less, 15% or less, 10% or less, 5% or less, 3% or less, or 1.5% or less, preferably 25% or less, 15% or less, or 10% or less. The method of making the volume ratio of particles of 1 μm or more in the application's sizing agent, as measured by laser diffraction scattering, fall within the above ranges is not limited, and, for example, the particles in the raw material and / or dispersion liquid can be made fine using a pulverizer or homogenizer, etc.

[0028] The volume median particle diameter of the application's sizing agent, as measured by laser diffraction scattering, can 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 can be 10 μm or less, 5 μm or less, 3 μm or less, 1 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, 0.3 μm or less, or 0.2 μm or less, preferably 1 μm or less. In the application, the volume median particle diameter refers to the median particle diameter (D50) in the particle size distribution on a volume basis, as measured by laser diffraction scattering.

[0029] The average particle diameter of the particles obtained by removing the liquid medium by natural drying at room temperature from the application's sizing agent (e.g., pulp oil-resistant agent) as a water-dispersible composition, as obtained from the observation image of a scanning electron microscope, can 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 can 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 form the above ranges of particle diameters, for example, the particles in the raw material and / or dispersion liquid can be made fine using a pulverizer or homogenizer, etc. Among these, room temperature refers to 20°C to 30°C, particularly 25°C.

[0030] The ion charge density of the dispersing agent of the present application can be -1000 μeq / g or more, -800 μeq / g or more, -600 μeq / g or more, -500 μeq / g or more, -400 μeq / g or more, -250 μeq / g or more, -100 μeq / g or more, -50 μeq / g or more, -25 μeq / g or more, 0 μeq / g or more, 1 μeq / g or more, 25 μeq / g or more, 50 μeq / g or more, 100 μeq / g or more, 200 μeq / g or more, preferably -600 μeq / g or more, for example, -400 μeq / g or more, -200 μeq / g or more, -50 μeq / g or more, and can be 5000 μeq / g or less, 2500 μeq / g or less, 1000 μeq / g or less, 750 μeq / g or less, 500 μeq / g or less, 400 μeq / g or less, 350 μeq / g or less, 300 μeq / g or less, 200 μeq / g or less, 100 μeq / g or less, or 50 μeq / g or less, preferably 1000 μeq / g or less, more preferably 500 μeq / g or less, for example, 300 μeq / g or less. It is particularly preferable that the ion charge density of the dispersing agent of the present application be -600 μeq / g or more and 100 μeq / g or less.

[0031] When the ion charge density of the dispersing agent has a negative value, for example, is less than -10 μeq / g, it is possible to impart an electric repulsive force to the dispersion, and to improve the stability of the aqueous dispersion. Furthermore, when the substrate has a positive charge, it is possible to improve the interaction with the substrate, and to improve the oil resistance during the treatment of the substrate. When the dispersing agent has a negative charge, the ion charge density thereof can be less than -20 μeq / g, less than -50 μeq / g, less than -75 μeq / g, or less than -100 μeq / g.

[0032] When the ion charge density of the dispersing agent is in the range of, for example, -10 μeq / g or more and less than 10 μeq / g, it is possible to suppress the aggregation when mixed with a medicament having a high charge.

[0033] When the ion charge density of the dispersing agent has a positive value, for example, is 10 μeq / g or more, it is possible to impart an electric repulsive force to the dispersion, and to improve the stability of the aqueous dispersion. Furthermore, when the substrate has a negative charge, it is possible to improve the interaction with the substrate, and to improve the oil resistance during the treatment of the substrate. When the dispersing agent has a positive charge, the ion charge density thereof 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.

[0034] The ion charge density of the dispersing agent of the present application can be measured, for example, by the following method.

[0035] The anion requirement amount is measured using a particle charge detector (BTG-made MUTEK PCD-04) for a sample liquid of 0.1 g / L of the solid content, using a prescribed 1 / 1000 potassium polyvinyl sulfonate solution, and the ionic charge density (cationic charge density) is calculated according to the following formula (1). Alternatively, instead of the potassium polyvinyl sulfonate solution, a polydiallyldimethylammonium chloride solution is used, and the cation requirement amount is similarly measured, and the ionic charge density (anionic charge density) is calculated according to the following formula (1).

[0036] Ionic charge density (μeq / g) = A / B (1) A: Cation requirement amount or anion requirement amount (μeq / L) B: Sample liquid concentration (g / L) Wax The releasing agent of the present application can contain a wax. The wax can be an organic substance that is solid at ordinary temperature and becomes liquid upon heating, and for example, the wax can be a hydrocarbon compound or a compound having a hydrocarbon group (e.g., an alkyl group) with a carbon atom number of 6 or more and 40 or less.

[0037] The wax of the present application adheres to a base material (particularly, a pulp base material), and can impart liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or stain resistance, to the base material.

[0038] The wax can be a compound having a monovalent hydrocarbon group with a carbon atom number of 1 or more and 40 or less, or a monovalent polysiloxane group, which can have a substituent. From the viewpoint of improving liquid repellency, the wax can have a hydrocarbon group (e.g., an alkyl group) with a carbon atom number of 6 or more and 40 or less.

[0039] Properties, etc. of wax The following illustrates properties, etc. that the wax can have.

[0040] The wax can be in a particulate shape (powder shape). The average particle diameter of the wax can 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 can be 10 μm or less, 5 μm or less, 3 μm or less, 1 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, 0.3 μm or less, or 0.2 μm or less, preferably 1 μm or less. The above particle diameter is a primary particle diameter. By being in the above range, the particulate stability is excellent, and the liquid-rewetting property can be made good. The average particle diameter can be measured by a microscope (scanning electron microscope). Specifically, a particulate sample of the wax is observed at an arbitrary magnification using a microscope. Next, in the case where the particulate shape is spherical, the diameter thereof is taken as the particle diameter, and in the case where the particulate shape is not spherical, the average of the longest diameter and the shortest diameter is taken as the particle diameter. The particle diameters of all the particles present in the field of view are measured, the field of view is moved, and the particle diameters are measured again, and by repeating the above operation, the particle diameters are measured at 100 points or more, and the average thereof is taken as the average particle diameter.

[0041] The wax of the present application is preferably a wax particle having a prescribed value for the volume-based presence ratio or the median particle diameter (D50) of the particles measured by laser diffraction scattering. Furthermore, the laser diffraction scattering method for the wax in the present application is performed in a dry or wet manner using a medium (e.g., water) that does not dissolve the wax. Furthermore, in the present application, the volume-based presence ratio and the median particle diameter (D50) of the wax measured by laser diffraction scattering and the volume-based presence ratio and the median particle diameter (D50) of the emulsion (water-dispersible composition) measured by laser diffraction scattering are generally not greatly different, and the difference therebetween can be ±30% or less, ±20% or less, ±10% or less, or ±5% or less.

[0042] The volume-based presence ratio of the particles of 100 μm or more of the wax of the present application measured by laser diffraction scattering can 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 can be 50% or less, 30% or less, 20% or less, 15% or less, 10% or less, 5% or less, 3% or less, or 1.5% or less, preferably 25% or less, 15% or less, or 10% or less. The method for bringing the volume-based presence ratio of the particles of 1 μm or more measured by laser diffraction scattering within the above range is not limited, and, for example, the particles in the raw material and / or the dispersion liquid can be made fine using a pulverizer or a homogenizer, etc.

[0043] The volume ratio of particles of 10 μm or more of the wax of the present application can 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 can 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 of bringing the volume ratio of particles of 1 μm or more within the above range by the laser diffraction scattering method is not limited, and, for example, the particles in the raw material and / or dispersion liquid can be micronized by using a pulverizer or a homogenizer, etc.

[0044] The volume median particle diameter of the wax of the present application can 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 can be 10 μm or less, 5 μm or less, 3 μm or less, 1 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, 0.3 μm or less, or 0.2 μm or less, preferably 1 μm or less. In the present application, the volume median particle diameter refers to the median particle diameter (D50) in the particle size distribution on a volume basis measured by the laser diffraction scattering method.

[0045] The HD (n-hexadecane) contact angle of the wax can 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, further preferably 30° or more, and can be 100° or less, 90° or less, or 75° or less. By bringing the HD contact angle of the wax to the above lower limit or more, the base material can be imparted with good liquid repellency (particularly oil repellency). The HD contact angle refers to the static contact angle for the spin-coated film of the wax, and refers to the value obtained by measuring the contact angle after 1 second of dropping 2 μL of HD on the spin-coated film.

[0046] The water contact angle of the wax can 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 can be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. By bringing the water contact angle of the wax to the above lower limit or more, the base material can be imparted with good liquid repellency (particularly water repellency). The water contact angle refers to the static contact angle for the spin-coated film of the wax, and refers to the value obtained by measuring the contact angle after 1 second of dropping 2 μL of water on the spin-coated film.

[0047] The wax can be a small molecule (e.g., a molecular weight of 1000 or less, or 500 or less), or a large molecule. When the wax is a large molecule, the weight average molecular weight thereof can be 1000 or more, 3000 or more, 5000 or more, 7500 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more, and can be 10000000 or less, 7500000 or less, 5000000 or less, 3000000 or less, 1000000 or less, 750000 or less, 500000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 10000 or less, 7500 or less, 5000 or less, or 3000 or less.

[0048] The melting point of the wax can 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, and preferably 40°C or more, 50°C or more, 60°C or more, 70°C or more, or 80°C or more, and can 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 can be measured according to JIS K 2235-1991.

[0049] [Structure of the wax, etc.] The wax of the present application can not have any of a fluorinated alkyl group having 8 or more carbon atoms, a perfluorinated alkyl group having 8 or more carbon atoms, a fluorinated alkyl group having 4 or more carbon atoms, a perfluorinated alkyl group having 4 or more carbon atoms, a perfluorinated alkyl group, a fluorinated alkyl group, and a fluorine atom. The wax can impart liquid repellency to the base material even if it does not contain these fluorine-containing groups.

[0050] The wax can be a hydrocarbon compound, or a compound having a monovalent hydrocarbon group having 1 or more and 40 or less carbon atoms, or a monovalent polysiloxane group, which can have a substituent. From the viewpoint of improving liquid repellency, the wax can be a hydrocarbon compound or a compound having a hydrocarbon group (e.g., an alkyl group) having 6 or more and 40 or less carbon atoms.

[0051] (Monvalent hydrocarbon group which can have a substituent) The wax can have a monovalent hydrocarbon group which can have a substituent.

[0052] The hydrocarbon group can be a monovalent hydrocarbon group having 1 or more and 40 or less carbon atoms. The hydrocarbon group can 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 can be branched, cyclic, or straight, and is more preferably straight.

[0053] The number of carbon atoms of the hydrocarbon group can 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 preferably 6 or more, 10 or more, 12 or more, or 16 or more, and can be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, and preferably 30 or less, 25 or less, or 20 or less.

[0054] The hydrocarbon group can have a substituent, but is preferably unsubstituted. As examples of the substituent, -OR', -N(R')2, -COOR', and a halogen atom, etc. (in the formula, R' is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms) can be listed. The substituent can have an active hydrogen or can not have an active hydrogen. The number of substituents can 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 with respect to the amount of carbon atoms and heteroatoms can be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, and preferably 75 mol% or more, and can be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less. For example, the hydrocarbon group can have 1 to 3 (e.g., 1) -OR' (particularly -OH) (e.g., other than at the terminal) as a substituent.

[0055] (Monomeric polysiloxane group) The wax can have a monomeric polysiloxane group. As with the (monomeric) hydrocarbon group, the (monomeric) polysiloxane group is capable of imparting liquid-repellency to the base material.

[0056] The polysiloxane group can be represented by the following formula: - [-Si(R s )2-O-] a - (In the formula, R s is independently at each occurrence a hydrocarbon group having 1 to 40 carbon atoms or a reactive group, a is an integer of 5 or more and 10,000 or less. R s is a hydrocarbon group having 1 to 40 carbon atoms or a reactive group.

[0057] As examples of the hydrocarbon group having 1 to 40 carbon atoms, a hydrocarbon group having 1 to 5 carbon atoms and a hydrocarbon group having 6 to 40 carbon atoms can be listed.

[0058] Examples of the hydrocarbon group having 1 to 5 carbon atoms include a hydrocarbon group having 1 to 5 carbon atoms (particularly an aliphatic hydrocarbon group, particularly an alkyl group, for example, a methyl group or an ethyl group, particularly a methyl group) such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group.

[0059] The hydrocarbon group having 6 to 40 carbon atoms can be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, preferably an aliphatic hydrocarbon group, particularly preferably a saturated aliphatic hydrocarbon group (an alkyl group). The hydrocarbon group can be cyclic, linear, branched, or linear. The number of carbon atoms of the hydrocarbon group can 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 can 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.

[0060] Examples of the reactive group include a group having a functional group (for example, a hydroxyl group, an amino group, a mercapto group, an epoxy group, a carboxyl group, a halogen-substituted alkyl group, a vinyl group, a (meth)acrylic acid group, a (meth)acryloxy group, and a (meth)acrylamide group, a hydrogen atom directly bonded to a silicon atom, and the like). The functional group can be directly bonded to the silicon atom, or can be bonded to an organic group directly bonded to the silicon atom. The organic group can be a hydrocarbon group, for example, can be an alkylene group or a divalent aromatic group. The number of carbon atoms of the hydrocarbon group can be 2 or more and 12 or less, and as the alkylene group, a group having 2 or more and 10 or less carbon atoms is preferable. As the divalent aromatic group, a group having 6 or more and 12 or less carbon atoms is preferable. The reactive group can be a group selected from a hydroxyl group, an epoxy ring, a carboxyl group, a (meth)acrylic acid group, and an amino group, for example, can be at least one selected from an epoxy ring, a hydroxyl group, a (meth)acrylic acid group, and a carboxyl group.

[0061] a can 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, preferably 10 or more, and can be 10000 or less, 7500 or less, 5000 or less, 3000 or less, 1500 or less, 1000 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less, preferably 500 or less.

[0062] R s The amount of R s 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 can be 100 mol% or less, 90 mol% or less, 80 mol% or less, or 70 mol% or less. For example, the amount of R sThe total of the R groups can be 50 mol% or more, 60 mol% or more, 70 mol% or more, 80 mol% or more, or 90 mol% or more methyl groups or ethyl groups (particularly methyl groups).

[0063] R as a hydrocarbon group having 6 to 40 carbon atoms in the polysiloxane group s The amount of R s The total of the R groups can be 3 mol% or more, 10 mol% or more, 20 mol% or more, or 30 mol% or more, and can be 100 mol% or less, 90 mol% or less, 80 mol% or less, or 70 mol% or less.

[0064] R as a reactive group in the polysiloxane group s The amount of R s The total of the R groups can be 5 mol% or more, 10 mol% or more, 20 mol% or more, or 30 mol% or more, and the total of the R groups can be 50 mol% or less, 40 mol% or less, 30 mol% or less, or 20 mol% or less.

[0065] R s The R s groups can be introduced in a random or block manner, and are preferably random.

[0066] The end structure of the above-described polysiloxane group is not limited, and can be -OR s , -Si(R s )3, or the like. The R s of the end structure can have one or more reactive groups. Examples of the reactive group are as described above, and can be at least one selected from the group consisting of an epoxy ring, a hydroxyl group, a (meth)acrylic acid group, and a carboxyl group, for example.

[0067] The polysiloxane group can have a linking group via which the raw material compound and the polysiloxane group are bonded, and as such a linking group, there is no limitation, and can be a hydrocarbon group having 1 to 40 (for example, 1 to 20) carbon atoms which can be interrupted by an oxygen atom, for example, a (poly)oxyalkylene group having 1 to 40 (for example, 1 to 20) carbon atoms.

[0068] Examples of the polysiloxane group can include: - [-Si(R a )2-O-] s -Si(R s1 )3 -L s - [-Si(R a )2-O-] s -Si(R s1 )3 -L s1 -O-L s - [-Si(R a )2-O-]a - R s - L s1 - [ - Si (R s ) 2 - O - ] n a - Si (R s ) 3 - L s1 - O - L s1 - [ - Si (R s ) 2 - O - ] n a - R s - L s1 - [ - Si (R s ) 2 - O - ] n a - Si (R s ) 3、 - L s1 - [ - Si (R s ) 2 - O - ] n a - R s [In the formula, R s independently at each occurrence is a hydrocarbon group having 1 to 40 carbon atoms or a reactive group, the terminal R s has one or more reactive groups, 50% by mole or more of the total R s groups are methyl groups, L s1 is a hydrocarbon group having 1 to 20 carbon atoms, a is 5 or more and 10,000 or less.] [In the formula, a represents an integer of 0 to 150, b represents an integer of 1 to 150, (a + b) is 5 to 200, and n is an integer of 0 to 36.]

[0069] [Examples of the wax] The wax can be a hydrocarbon compound or a compound having a hydrocarbon group. Examples of the hydrocarbon group, the preferable range, etc. are as described above, and for example, the hydrocarbon group can be a hydrocarbon group having 6 or more and 40 or less carbon atoms.

[0070] As examples of the wax, there can be mentioned: hydrocarbon waxes (paraffin, polyolefin, etc.), non-hydrocarbon waxes, polymer waxes (vinyl polymer, silicone wax, etc.), and the like.

[0071] There can be mentioned: petroleum waxes such as paraffin wax, microcrystalline wax, montan wax, ozokerite, white ozokerite, and petrolatum wax; Synthetic waxes such as a Fischer-Tropsch wax, a polyethylene wax, a polypropylene wax, an acrylic polymer wax, a polytetrafluoroethylene wax, a silicone wax, and the like.

[0072] The wax can be a hydrocarbon compound.

[0073] [Amount of wax] The amount of the wax in the release agent can 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 can 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. The wax can be used alone as the release agent.

[0074] [Dispersant] The release agent of the present application can contain a dispersant. The dispersant can be at least one selected from the group consisting of an organic dispersant and an inorganic dispersant. The dispersant can be at least one selected from the group consisting of an anionic dispersant, a nonionic dispersant, a cationic dispersant, an amphoteric dispersant, and an inorganic dispersant.

[0075] The dispersant can use the organic dispersant and the inorganic dispersant respectively, or can be a combination of the organic dispersant and the inorganic dispersant.

[0076] As the dispersant, an organic dispersant can be used. The organic dispersant can be classified into a nonionic dispersant, an anionic dispersant, a cationic dispersant, and an amphoteric dispersant, and the organic dispersant can refer to a surfactant.

[0077] The dispersant can be a non-fluorine dispersant.

[0078] [Nonionic dispersant] The dispersant can contain a nonionic dispersant. The nonionic dispersant can be a nonionic surfactant.

[0079] The nonionic dispersant can be a low-molecular type or a high-molecular type. The molecular weight can be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and can be 100000 or less, 10000 or less, 7500 or less, 5000 or less, 25000 or less, 750 or less, or 250 or less.

[0080] As examples of the nonionic dispersant, ethers, esters, ester ethers, alkylol amides, polyhydric alcohol, and amine oxides can be listed.

[0081] Examples of ethers are compounds having an oxyalkylene group (preferably a polyoxyethylene group).

[0082] Examples of esters are esters of alcohols and fatty acids. Examples of alcohols are 1- to 30-membered (particularly 2- to 10-membered) alcohols having 1 to 50 carbon atoms (particularly 10 to 30 carbon atoms) (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0083] Examples of ester ethers are compounds obtained by adding an alkylene oxide (particularly ethylene oxide) to esters of alcohols and fatty acids. Examples of alcohols are 1- to 30-membered (particularly 2- to 10-membered) alcohols having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms) (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0084] Examples of alkanolamides are formed from fatty acids and alkanolamines. The alkanolamides can be monoalkanolamides or dialkanolamides. Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. The alkanolamines can be alkanols having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0085] The polyhydric alcohol can be a 2- to 5-membered alcohol having 10 to 30 carbon atoms.

[0086] The amine oxide can be an oxide of an amine (secondary amine or preferably tertiary amine) (e.g., having 5 to 50 carbon atoms).

[0087] The nonionic dispersant is preferably a nonionic dispersant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms of 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.

[0088] The nonionic dispersant is selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, and amine oxides, and is preferably a nonionic dispersant having an oxyalkylene group.

[0089] The nonionic dispersing agent can be an alkylene oxide adduct of a straight-chain and / or branched-chain aliphatic (saturated and / or unsaturated) group, a polyalkylene glycol ester of a straight-chain and / or branched-chain aliphatic acid (saturated and / or unsaturated), a sorbitan ester of a straight-chain and / or branched-chain aliphatic acid (saturated and / or unsaturated), a glycerin ester of a straight-chain and / or branched-chain aliphatic acid (saturated and / or unsaturated), a polyglycerin ester of a straight-chain and / or branched-chain aliphatic acid (saturated and / or unsaturated), a sucrose ester of a straight-chain and / or branched-chain aliphatic acid (saturated and / or unsaturated), a polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of acetylene glycol, or the like. Among these, the structure of the alkylene oxide adduct portion and the polyalkylene glycol portion is preferably a polyoxyethylene (POE) or a polyoxypropylene (POP) or a POE / POP copolymer (which can be a random copolymer or a block copolymer).

[0090] In addition, the nonionic dispersing agent can not contain an aromatic group.

[0091] The nonionic dispersing agent can be a compound represented by the formula: 1 O— (CH2CH2O) p — (R 2 O) q — R 3 .

[0092] [In the formula, R 1 is an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms or an acyl group, R 2 are each independently the same or different and are an alkylene group having 3 or more (for example, 3 to 10) carbon atoms, R 3 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms, p is a number of 2 or more, q is 0 or a number of 1 or more.] R 1 is preferably 8 to 20, and particularly 10 to 18. As a preferable specific example of R 1 , octyl, nonyl, trimethylnonyl, lauryl, tridecyl, oleyl, and stearyl can be given.

[0093] Examples of R 2 are propylene and butylene.

[0094] In the nonionic dispersing agent, p can be a number of 3 or more (for example, 5 to 200). q can be a number of 2 or more (for example, 5 to 200). That is, — (R 2 O) q — can form a polyoxyalkylene chain.

[0095] The nonionic dispersant can be a polyoxyethylene alkylene alkyl ether having a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) in the middle. As the hydrophobic oxyalkylene chain, an oxypropylene chain, an oxybutylene chain, a styrene chain, and the like can be exemplified, of which an oxypropylene chain is preferred.

[0096] Specific examples of the nonionic dispersant include condensation products of ethylene oxide with hexylphenol, isooctylphenol, hexadecanol, oleic acid, alkanes (C 12 - C 16 )thiol, sorbitan monofatty acid (C7-C 19 ) or alkyl (C 12 - C 18 )amine, etc., sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, lecithin derivatives, and the like. As an example of the nonionic dispersant, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene polyoxybutylene alkyl ethers, polyoxyethylene polyoxypropylene glycols, polyethylene imine ethoxylates, and the like can be exemplified.

[0097] The proportion of the polyoxyethylene block with respect to the molecular weight of the nonionic dispersant (copolymer) is 5 to 80% by weight, for example, 30 to 75% by weight, particularly 40 to 70% by weight.

[0098] The average molecular weight of the nonionic dispersant is generally 300 to 5,000, for example, 500 to 3,000.

[0099] The nonionic dispersant can be a single one or a mixture of two or more. The nonionic dispersant can be a mixture of a compound having an HLB (hydrophilic-lipophilic balance) of less than 15 (particularly 5 or less) and a compound having an HLB of 15 or more. Specifically, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene, polyoxypropylene, sorbitan fatty acid esters having an HLB of less than 7, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters having an HLB of 1 to 18 are preferred.

[0100] [Nonionic Dispersant] The dispersant can contain a nonionic dispersant. The nonionic dispersant can be a nonionic surfactant. The nonionic dispersant can be a compound having no amide group.

[0101] The cationic dispersant can be low-molecular (e.g., molecular weight 2000 or less, particularly 10000 or less) or high-molecular (e.g., molecular weight 2000 or more). The cationic dispersant can have a molecular weight of 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and can have a molecular weight of 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.

[0102] The cationic dispersant can be an aliphatic or aromatic dispersant, and examples include ammonium salts (e.g., quaternary ammonium salts) and the like. The cationic dispersant can be an oxyethylene-addition-type ammonium salt. Specifically, examples include amine salt-type dispersants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, and the like; quaternary ammonium salt-type dispersants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzalkonium chloride, benzethonium chloride, and the like; and high-molecular cationic dispersants such as polyquaternium-1 to 47, and the like. As an example of a cationic dispersant, mention can be made of alkylamine salts, quaternary ammonium salts, and the like.

[0103] The low-molecular cationic dispersant can be R 21 -N ＋ (-R 22 )(-R 23 )(-R 24 )X － [wherein R 21 , R 22 , R 23 , and R 24 are hydrogen or a hydrocarbon group having 1 to 40 carbon atoms, and X is an anionic group].

[0104] Specific examples of R 21 , R 22 , R 23 , and R 24 are alkyl groups (e.g., methyl, butyl, stearyl, palmitoyl), aromatic groups (e.g., benzyl, phenyl), and the like. Specific examples of X are halogens (e.g., chlorine), acids (e.g., hydrochloric acid, acetic acid). As an example of a cationic dispersant, mention can be made of monoalkyltrimethylammonium salts (alkyl group having 4 to 40 carbon atoms), benzalkonium chloride, and the like.

[0105] Specifically, the low-molecular cationic dispersant can be a compound represented by the formula R 1 p -N ＋ R 2q X － The ammonium salt shown.

[0106] [In the formula, R] 1 For C12 and above (e.g., C 12 ~C 50 Straight-chain and / or branched aliphatic (saturated and / or unsaturated) groups, R 2 It is an alkyl, benzyl, or polyoxyethylene group of H or C1 to C4 (the number of oxyethylene groups is, for example, 1 (especially 2, especially 3) to 50) (particularly preferred CH3, C2H5). X is a halogen atom (e.g., chlorine), or a C1-C4 fatty acid salt, or a C1-C4 sulfonate. p is 1 or 2, q is 2 or 3, and p + q = 4. R 1 The number of carbon atoms can be 12 to 50, for example 12 to 30.

[0107] Low molecular weight cationic dispersants may include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyl di(hydrogen polyoxyethylene)ammonium chloride, benzyldodecyl di(hydrogen polyoxyethylene)ammonium chloride, N-[2-(diethylamino)ethyl]oleamide hydrochloride, etc.

[0108] High molecular weight cationic dispersants can be various polymers (e.g., polyquaternium salts-1 to 47) having cationic groups (e.g., ammonium groups, quaternary ammonium groups). Examples of high molecular weight cationic dispersants include cationic starch, cationic cellulose (e.g., chloro-O-(2-hydroxy-3-(trimethylammonium)propylhydroxyethyl cellulose), cationic guar gum, cationic xanthan gum, chitosan, and other cationic natural products (especially cationic sugars); polymers of monomers containing cationic groups such as aziridine, vinylimidazole, aminoalkyl methacrylate, N,N,N',N'-tetramethyl-2-butene-1,4-diamine, quaternized dimethylammonium ethyl methacrylate, diallyl dimethylammonium chloride, dimethylaminopropylamine, and quaternized vinylimidazole.

[0109] [Anionic dispersant] Dispersants may contain anionic dispersants. Anionic dispersants may be anionic surfactants. Dispersants may also not contain anionic dispersants.

[0110] The anionic dispersant can be low-molecular or high-molecular. The molecular weight can be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and can be 100000 or less, 10000 or less, 7500 or less, 5000 or less, 25000 or less, 750 or less, or 250 or less.

[0111] Examples of the anionic dispersant include alkyl ether sulfate, alkyl sulfate, alkenyl ether sulfate, alkenyl sulfate, olefin sulfonate, alkane sulfonate, saturated or unsaturated fatty acid salt, alkyl or alkenyl ether carboxylic acid salt, a- sulfonated fatty acid salt, N-acyl amino acid type dispersant, phosphoric acid monoester type dispersant or diester type dispersant, and sulfosuccinic acid ester. As an example of the anionic dispersant, carboxylic acid salt (e.g., fatty acid salt) and the like can be mentioned.

[0112] [Amphoteric dispersant] The dispersant can include an amphoteric dispersant. The amphoteric dispersant can be an amphoteric surfactant.

[0113] The amphoteric dispersant can be low-molecular or high-molecular. The molecular weight can be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and can be 100000 or less, 10000 or less, 7500 or less, 5000 or less, 25000 or less, 750 or less, or 250 or less.

[0114] Examples of the amphoteric dispersant include alanine type, imidazoline betaine type, amide betaine type, betaine acetate, and the like, and specifically, lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazoline betaine, lauryl dimethylamino acetic acid betaine, fatty acid amide propyl dimethylamino acetic acid betaine, and the like can be mentioned.

[0115] [Inorganic dispersant] The dispersant can include an inorganic dispersant.

[0116] The average primary particle diameter of the inorganic dispersant can 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 can be 100 μm or less, 50 μm or less, 10 μm or less, 1 μm or less, 500 nm or less, or 300 nm or less. The average primary particle diameter can be measured, for example, by observation with a microscope (scanning electron microscope or transmission electron microscope). The inorganic dispersant can be a hydrophilic particle.

[0117] Examples of the inorganic dispersing agent include phosphoric acid polyvalent metal salts 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; hydroxides such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide; and the like.

[0118] [Amount of dispersing agent] The amount of the dispersing agent can be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, and can 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, relative to 100 parts by weight of the wax.

[0119] [liquid medium] The polish of the present application can contain a liquid medium. The liquid medium can be water, an organic solvent, or a mixture of water and an organic solvent. The polish can be a dispersion liquid or a solution. The polish of the present application can contain at least water.

[0120] Examples of the organic solvent are 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 can contain a compound having at least one hydroxyl group (e.g., a polyhydric alcohol such as an alcohol, a glycol-based solvent, and the like, an ether of a polyhydric alcohol (e.g., a monoether), and the like). These can be used alone or in combination of two or more.

[0121] [Amount of liquid medium] The amount of the liquid medium can be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, or 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, relative to 1 part by weight of the wax 1, and can 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.

[0122] The amount of the water can 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, relative to 1 part by weight of the wax 1, and can 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.

[0123] The amount of the organic solvent can 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, relative to 1 part by weight of the wax 1, and can 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.

[0124] 〔Organic Silicon〕 The application agent of the present application can contain an organic silicon (polyorganosiloxane). By containing an organic silicon, in addition to good liquid-repellent properties, a good hand feeling, durability can also be well balanced.

[0125] As the organic silicon, a publicly known organic silicon can be used, and as examples of the organic silicon, polydimethylsiloxane, modified organic silicon (amino-modified, epoxy-modified organic silicon, carboxyl-modified organic silicon, methyl hydrogen-containing organic silicon, etc.) can be listed. The organic silicon can be an organic silicon wax having a property similar to a wax. These can be used alone or in combination of two or more.

[0126] The weight average molecular weight of the organic silicon can be 1000 or more, 10000 or more, or 50000 or more. The weight average molecular weight of the organic silicon can be 500000 or less, 2500000 or less, 100000 or less, or 50000 or less.

[0127] [Amount of organic silicon] The amount of the organic silicon can 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 can 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, with respect to 100 parts by weight of the wax.

[0128] [Organic acid] The polish of the present application can contain an organic acid. As the organic acid, a publicly known acid can be used. As examples of the organic acid, carboxylic acid, sulfonic acid, sulfinic acid, etc. are preferably listed, and carboxylic acid is particularly preferable. As examples of the carboxylic acid, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid, etc. can be listed, and formic acid or acetic acid is particularly preferable. In the present application, one kind of organic acid can be used, or two or more kinds of organic acids can be used in combination. For example, formic acid and acetic acid can be used in combination. By adding the organic acid, the stability of the water dispersion can be improved.

[0129] [Amount of organic acid] The amount of the organic acid can 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 can 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, with respect to 100 parts by weight of the wax. The amount of the organic acid can be adjusted so that the pH of the polish becomes 3 to 10, for example, 5 to 9, particularly 6 to 8. The polish can be acidic (pH 7 or less, for example, 6 or less).

[0130] 〔Inorganic acid〕 The dope of the present application can contain an inorganic acid. As the inorganic acid, a publicly known acid can be used. As examples of the inorganic acid, hydrogen chloride, hydrogen bromide, hydrogen iodide, nitric acid, boric acid, sulfuric acid, phosphoric acid, and the like can be listed. In the present application, one kind of inorganic acid can be used, or two or more kinds of inorganic acids can be used in combination. By adding the inorganic acid, the stability of the aqueous dispersion can be improved.

[0131] [Amount of inorganic acid] The amount of the inorganic acid can 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 can 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, with respect to 100 parts by weight of the wax. The amount of the inorganic acid can be adjusted in such a manner that the pH of the dope becomes 3 to 10, for example, 5 to 9, particularly 6 to 8. The dope can be acidic (pH 7 or less, for example, 6 or less).

[0132] 〔Curing agent〕 The dope of the present application can contain a curing agent (active hydrogen reactive compound or active hydrogen-containing compound).

[0133] The curing agent (crosslinking agent) in the dope can allow the dope to be well cured. The curing agent can be an active hydrogen reactive compound or an active hydrogen-containing compound which reacts with an active hydrogen or an active hydrogen reactive group. Examples of the active hydrogen reactive compound are isocyanate compounds, epoxy compounds, chlorine-methyl-containing compounds, carboxyl-containing compounds, and hydrazide compounds. Examples of the active hydrogen-containing compound are hydroxyl-containing compounds, amino-containing compounds, and carboxyl-containing compounds, ketone-containing compounds, hydrazide compounds, and melamine compounds.

[0134] The curing agent can contain an isocyanate compound. The isocyanate compound can be a polyisocyanate compound. The polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound functions as a crosslinking agent. Examples of the polyisocyanate compound can be listed aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic aliphatic polyisocyanate, aromatic polyisocyanate, and derivatives of these polyisocyanates, and the like. The isocyanate compound can be a blocked isocyanate compound (for example, blocked polyisocyanate compound). The blocked isocyanate compound is a compound which inhibits the reaction by masking the isocyanate group of the isocyanate compound with a blocking agent.

[0135] Examples of the aliphatic polyisocyanate are aliphatic diisocyanates such as 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-diisocyanatomethylhexanoate, and lysine ester triisocyanate, aliphatic triisocyanates such as 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, and the like. These can be used alone or in combination of two or more.

[0136] Examples of the alicyclic polyisocyanate are alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of the alicyclic polyisocyanate are 1,3-cyclopentylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 1,3,5-triisocyanatocyclohexane. These can be used alone or in combination of two or more.

[0137] Examples of the aromatic aliphatic polyisocyanate are aromatic aliphatic diisocyanates and aromatic aliphatic triisocyanates. Specific examples of the aromatic aliphatic 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, 1,3,5-triisocyanatomethylbenzene. These can be used alone or in combination of two or more.

[0138] Examples of the aromatic polyisocyanate are aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of the aromatic polyisocyanate 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-toluene diisocyanate or a mixture thereof, triphenylmethane-4,4',4"-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate, and the like. These can be used alone or in combination of two or more.

[0139] Examples of derivatives of polyisocyanate include various derivatives of the above-mentioned polyisocyanate compounds, such as dimers, trimers, biurets, allophanates, carbodiimides, uretdiones, uretonimines, isocyanurates, iminooxadiazinediones, and the like. These can be used alone or in combination with two or more.

[0140] These polyisocyanates can be used singly or in combination with two or more.

[0141] As the polyisocyanate compound, it is preferable to use a compound in which the isocyanate groups of the polyisocyanate compound are capped with a capping agent, i.e., a blocked polyisocyanate compound (blocked isocyanate). For the reason that it is relatively stable in solution, it can be used in the same solution as the release agent, and the like, it is preferable to use a blocked polyisocyanate compound.

[0142] The capping agent blocks the free isocyanate groups. The blocked polyisocyanate compound can regenerate the isocyanate groups by heating to 100°C or higher, for example, 130°C or higher, and easily reacts with the hydroxyl groups. Examples of the capping agent are phenol-based compounds, lactam-based compounds, aliphatic alcohol-based compounds, oxime-based compounds, and the like. The polyisocyanate compound can be used singly or in combination with two or more.

[0143] The epoxy compound is a compound having an epoxy group. Examples of the epoxy compound are epoxy compounds having a polyoxyalkylene group, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether, and the like.

[0144] The chloromethyl group-containing compound is a compound having a chloromethyl group. Examples of the chloromethyl group-containing compound are chloromethyl polystyrene, and the like.

[0145] The carboxyl group-containing compound is a compound having a carboxyl group. Examples of the carboxyl group-containing compound are (poly)acrylic acid, (poly)methacrylic acid, and the like.

[0146] As specific examples of the ketone group-containing compound, (poly)bisacetonitrile acrylamide, bisacetonitrile alcohol, and the like can be mentioned.

[0147] As specific examples of the hydrazine compound, hydrazine, carbohydrazide, adipic acid dihydrazide, and the like can be mentioned.

[0148] Specific examples of the melamine compound include melamine resin, methyl etherified melamine resin, and the like.

[0149] [Amount of Curing Agent] The amount of the curing agent can be 0.1 parts by weight or more, 1 parts 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, or 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 can 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.

[0150] [Other ingredients] The agent can contain other ingredients in addition to the above-mentioned ingredients. As examples of the other ingredients, polysaccharides, paper strength (reinforcing) agents, coagulants, retention agents, coagulants, adhesive resins, anti-slip agents, sizing agents (sizing agents), paper strength enhancers, fillers, antistatic agents, preservatives, ultraviolet absorbers, antibacterial agents, deodorants, perfumes, and the like can be listed. These can be used alone or in combination of two or more. In addition to the above-mentioned ingredients, as the other ingredients, other water- and / or oil-repellent agents, dispersants, hand adjusters, softening agents, flame retardants, coating fixatives, anti-wrinkling agents, drying speed adjusters, crosslinking agents, film-forming aids, compatibilizers, antifreezes, viscosity adjusters, ultraviolet absorbers, antioxidants, pH adjusters, insect repellents, antifoaming agents, shrinkage preventives, washing anti-wrinkling agents, shape retainers, drape retainers, ironing property improvers, whitening agents, whitening agents, fabric softening clays, polyvinylpyrrolidone, and the like, antitransfer agents, high-molecular dispersants, stain release agents, scum dispersants, fluorescent brighteners such as 4,4-bis(2-sulfostyryl) biphenyl disodium (Tinopal CBS-X manufactured by Ciba), dye fixatives, anti-fading agents such as 1,4-bis(3-aminopropyl) piperazine, bleaching agents, enzymes such as cellulase, amylase, protease, lipase, and keratinase as fiber surface modifiers, foam suppressors, silk fibroin powder as a component capable of imparting a silk-like hand and function such as moisture absorption and release, these surface modifiers or emulsified dispersions (for example, K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical), hydrolyzed silk liquid (Kamoi), Silkgen G Soluble S (ICHIMARU PHARCOS Co., Ltd.)), anti-pollution agents (for example, nonionic high-molecular compounds formed of an alkylene terephthalate and / or an alkylene isophthalate unit and a polyoxyalkylene unit (for example, FR627 manufactured by Musashino Chemical Co., SRC-1 manufactured by Clariant Japan), and the like can be used. These can be used alone or in combination of two or more.

[0151] [Amount of other ingredients] The amount of each of the other components or the total amount thereof can be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the wax, and can 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.

[0152] The pulp composition of the present application contains pulp and a lubricant component. The pulp composition of the present application is obtained by treating pulp with a lubricant.

[0153] The pulp composition contains pulp, which is treated as a pulp base material with a lubricant. The pulp base material can be in the form of pure pulp, pulp slurry, pulp products, and the like, and as examples of the pulp base material, there can be mentioned pulp such as bleached or unbleached chemical pulp of 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-mentioned pulp; waste paper pulp such as waste newspaper, waste magazine paper, waste corrugated paper, or deinked waste paper; and pulp products such as paper, paper containers, paper molded bodies, and the like, formed of paper. As specific examples of the pulp products, there can be mentioned food packaging materials, food containers, plasterboard base paper, coating base paper, medium paper, ordinary liner paper, and medium cores, neutral pure white wrapping paper, neutral liner paper, rust-proof liner paper, and metal composite paper, kraft paper, neutral printing and writing paper, neutral coating base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper, and neutral information paper, molded paper (molded containers), and the like. As examples of suitable pulp products, there can be mentioned food packaging materials and food containers, and in particular, pulp molded products for food contact applications.

[0154] ​​The amount of pulp in the pulp composition can 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 can 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 can be 75% by weight or more.

[0155] [liquid medium] The pulp composition can include a liquid medium. The liquid medium can be water, an organic solvent, or a mixture of water and an organic solvent, typically an aqueous medium, particularly water. The liquid medium can include a liquid medium from the release agent.

[0156] [amount of liquid medium] The amount of liquid medium in the pulp composition can 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 can 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 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 liquid medium in the pulp composition is 30% by weight or less, particularly 10% by weight or less.

[0157] [release agent] The pulp composition can include a wax in the release agent. The release agent is described in detail in <Release Agent> in addition.

[0158] [amount of release agent] The amount of the additive added to the pulp base material can be adjusted so that the wax is in the desired amount. The amount of the wax can 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 can 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, with respect to the pulp.

[0159] In the external addition treatment, the amount of the wax contained in the coating layer can be 0.01 g / m 2 or more, 0.03 g / m 2 or more, 0.05 g / m 2 or more, 0.1 g / m 2 or more, 0.3 g / m 2 or more, 0.5 g / m 2 or more, or 1.0 g / m 2 or more, and can be 5.0 g / m 2 or less, 4.0 g / m 2 or less, 3.0 g / m 2 or less, 2.0 g / m 2 or less, 1.0 g / m 2 or less, 0.5 g / m 2 or less, 0.3 g / m 2 or less, or 0.1 g / m 2 or less.

[0160] 〔Paper strength (reinforcing) agent〕 The pulp composition can contain a paper strength (reinforcing) agent. As examples of the paper strength (reinforcing) agent, the following can be listed: polyacrylamide-based paper strength reinforcing agents such as cationic polyacrylamide, anionic polyacrylamide, amphoteric polyacrylamide, and the like; polysaccharide-based paper strength reinforcing agents such as starch, enzyme-denatured starch, thermochemically-denatured starch, oxidized starch, esterified starch, etherified starch (e.g., hydroxyethylated starch, and the like), aldehyde starch, cationized starch, starch, xanthan gum, gum karaya, welan gum, guar gum, pectin, tamarind gum, carrageenan, chitosan, gum arabic, locust bean gum, cellulose, alginic acid, agar, dextran, cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, chitin nanofiber, cellulose nanofiber, and pullulan, modified polysaccharides of these (e.g., modified polysaccharides into which a hydroxyl group or a cationic group is introduced), and the like; polyamide resins, polyamine resins, polyamide-polyamine resins, polyamide-epichlorohydrin resins, polyamide-polyamine-epichlorohydrin resins, polyamide-polyurea-formaldehyde resins, epoxidized polyamide resins, and the like; urea resins, melamine resins, urea-formaldehyde resins, melamine-formaldehyde resins, and the like; polyvinyl alcohol resins, fully saponified polyvinyl alcohol resins, partially saponified polyvinyl alcohol resins, carboxyl-modified polyvinyl alcohol resins, silanol-modified polyvinyl alcohol resins, cation-modified polyvinyl alcohol resins, terminal alkyl-modified polyvinyl alcohol resins, and the like; styrene-butadiene copolymers, polyvinyl acetate, vinyl chloride-vinyl acetate copolymers, polyvinyl chloride, polyvinylidene chloride, polyacrylate, aliphatic acid diamide, polyethylene imine resins, ketone aldehyde resins, and the like. As the paper strength agent in the present application, a polyacrylamide-based paper strength agent, a polysaccharide-based paper strength agent, or a polyamide-based paper strength agent is preferred.

[0161] [Amount of paper strength agent] The amount of the paper strength agent with respect to the pulp can 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 can 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.

[0162] [Size agent] The pulp composition can contain a size agent. As examples of the size agent, cationic size agents, anionic size agents, neutral size agents, amphoteric size agents, for example, rosin-based size agents (e.g., acidic rosin-based size agents, neutral rosin-based size agents), alkyl alkene ketone dimers, alkenyl succinic anhydrides, and the like can be listed.

[0163] [Amount of size agent] The amount of the size agent with respect to the pulp can 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 can 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.

[0164] [Other additives] In the pulp composition, in addition to the above-mentioned components, additives used in the production of pulp products, such as a fixing agent (aluminum sulfate (alum), etc.), an organic acid (formic acid, acetic acid, etc.), a coagulating agent, a retention aid, a dye, a fluorescent dye, a pitch control agent, an antifoaming agent, etc., can be further contained. The pulp composition contains components from the size agent, but each component that the above-mentioned size agent can contain can be added to the pulp composition as an additive.

[0165] The amount of the above-mentioned additive with respect to the pulp can be 0.1% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, and can 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, respectively.

[0166] <Method for producing a pulp product> The method for producing a pulp product in the present application can include a step of treating a pulp substrate with a size agent. The pulp substrate is treated with the size agent to obtain a pulp composition. As needed, by performing a treatment step such as drying, heating, molding, etc. on the obtained pulp composition, a pulp product can be obtained.

[0167] The above-mentioned description of the "pulp composition" is cited with respect to the kind and composition of the pulp substrate and the size agent. The size agent of the present application can be applied to a substrate as a treatment agent (particularly, a surface treatment agent) by a method known in the art. As the method of treatment, a method of diluting the size agent of the present application as needed in an organic solvent or water, and adhering to the inside and / or surface of the pulp substrate and drying by a known method such as dip coating, spray coating, and foam coating, etc. can be used. After drying, a pulp product to which the solid component in the size agent is adhered is obtained. In addition, as needed, it can be applied together with a suitable crosslinking agent, and cured. The concentration of the size agent in the treatment agent in contact with the pulp substrate can be appropriately changed depending on the use, and can be 0.01 to 10% by weight, for example, 0.05 to 5% by weight.

[0168] The size agent can be applied to the pulp substrate by any known method for treating a pulp substrate with a liquid. The pulp substrate can be immersed in the size agent, the pulp substrate can be mixed with the size agent, or the pulp substrate can be attached or sprayed with the solution. The treated pulp substrate is preferably dried and cured by heating in order to exhibit liquid repellency. The heating temperature can be, for example, 100°C to 200°C, 100°C to 170°C, or 100°C to 120°C. The heating time in the present application can be 5 seconds to 60 minutes, for example, 30 seconds to 3 minutes.

[0169] As the treatment method of the pulp base material, an internal addition treatment method of adding a debonder to the pulp before papermaking (e.g., pulp slurry) or an external addition treatment method of applying a debonder to the pulp after papermaking (e.g., paper product) can be used. As examples of the internal addition treatment method, mixing, impregnation, and the like can be listed, and a process of adding a debonder to the pulp slurry and stirring and mixing can be included. As examples of the external addition treatment method, spraying, coating, and the like can be listed, and specifically, a pond type two-roll size press, a dam roll type, and a rod type metering size press, and the like can be listed. The treatment can be external addition treatment or internal addition treatment. For example, when the pulp base material is paper, the paper can be coated, or the paper can be attached or sprayed with a solution, or mixed with the pulp slurry before papermaking to be treated.

[0170] The treatment method can be an internal addition treatment of adding a debonder to the pulp slurry before papermaking. As the internal addition treatment, one or more of the following processes can be included: a process of adding a debonder to the pulp slurry and stirring and mixing; a process of suction dewatering the pulp composition prepared by the process through a net-shaped body of a prescribed shape, allowing the pulp composition to accumulate, and forming a pulp molded product intermediate; and a process of performing molding drying on the pulp molded product intermediate through a molded die after heating, thereby obtaining a pulp molded product, but is not limited thereto. The treated paper can be simply dried at room temperature or at a high temperature, and heat treatment can be optionally performed depending on the properties of the paper. The temperature of the heat treatment can be 150°C or higher, 180°C or higher, or 210°C or higher, and can be 300°C or lower, 250°C or lower, or 200°C or lower, and in particular, 80°C to 180°C. By performing heat treatment in such a temperature range, excellent oil resistance and water resistance, and the like can be exhibited. The pulp base material subjected to the internal addition treatment can be subjected to external addition treatment and treated with a debonder, and another wax and another paper strength enhancer can be attached to the surface.

[0171] The treatment method can be an external addition treatment of applying a size agent to a paper pulp base after papermaking. The size press of the external addition treatment can be classified into the following methods according to the coating method. One coating method is a so-called pond type two-roll size press in which a coating liquid (size liquid) is supplied to a nip formed by passing paper between two rubber rolls, a coating liquid accumulation portion called a pond is formed, and the size liquid is coated on both sides of the paper in the coating liquid accumulation portion. Other coating methods include a dam roll type in which the size liquid is coated by a surface transfer die and a rod type metering size press. In the pond type two-roll size press, the size liquid easily penetrates into the inside of the paper, and in the surface transfer die, the size liquid components easily remain on the surface of the paper. In the surface transfer die, the coating layer easily remains on the surface of the paper compared to the pond type two-roll size press, and the coating layer formed on the surface is more than that of the pond type two-roll size press. In the present application, even in the case of using the above-described pond type two-roll size press, the paper can be imparted with properties. The paper thus treated is subjected to simple drying at room temperature or at a high temperature, and then, optionally, depending on the properties of the paper, heat treatment at a temperature range of up to 300°C, for example, up to 200°C, particularly, 80°C to 180°C, and can exhibit excellent oil resistance and water resistance and the like.

[0172] Examples Hereinafter, the present application will be described in detail with examples, but the present application is not limited to these examples.

[0173] < Test Method > The steps of the test are described below.

[0174] [Volume Existence Ratio of Particles and Median Particle Diameter (D50)] The volume existence ratio of particles of 100 μm or more, the volume existence ratio of particles of 10 μm or more, and the median particle diameter (D50) were calculated from the frequency distribution (volume distribution) on a volume basis measured by a laser diffraction / scattering device for the wax and water dispersion.

[0175] [Mean Particle Diameter of Particles Obtained by Removing Liquid Medium from Oil-Resistant Agent] The concentration of the water dispersion of the oil-resistant agent was adjusted to 1 wt%. The water dispersion was cast on an aluminum foil, dried at room temperature for 1 day, and the liquid medium was removed, thereby producing an observation sample. The observation sample was observed by a scanning electron microscope, an observation image was obtained, and particle diameter observation was performed. When the particle shape was spherical, the diameter thereof was taken as the particle diameter, and when the particle shape was non-spherical, the average of the longest diameter and the shortest diameter was taken as the particle diameter. The particle diameters of all particles present in the field of view were measured, the field of view was moved, the particle diameters were measured again, and the operation was repeated, thereby measuring the particle diameters of 100 points or more, and the average thereof was taken as the mean particle diameter of the particles obtained by removing the liquid medium from the oil-resistant agent.

[0176] [Production of Paper Pulp Moldings] The pulp was molded using an automatic molding machine. A net body was disposed on a metal pulp molding mold having a plurality of suction holes in the lower portion, a metal tank was disposed in the upper portion, and a mixture of pulp slurry and water-dispersible oil repellent (pulp composition) was added to the metal tank in the upper portion. The pulp composition was suctioned through the pulp molding mold and the net body from the side opposite to the side on which the net body was disposed using a vacuum pump, and dehydrated, so that the solid components (pulp, etc.) contained in the pulp composition were deposited on the net body, and a pulp molding intermediate was obtained. Subsequently, the obtained pulp molding intermediate was dried in a metal concave-convex molding mold heated to 60 to 250°C under a pressure of 0.05 to 5 MPa from the top and bottom. Thus, a pulp molding product shaped as a container was produced.

[0177] [Oil resistance test] Corn oil at 50°C was injected into the pulp molding at 100 mL, and after left standing at room temperature for 45 minutes, the corn oil was removed from the pulp molding, and the degree of oil penetration of the pulp molding was evaluated. According to the degree of penetration, the evaluation value was set as described below.

[0178] 5: No oil penetration on the inside.

[0179] 4: Oil penetration on the inside. No oil penetration on the back.

[0180] 3: Oil penetration on the inside. Slight oil penetration on the back.

[0181] 2: Oil penetration on the inside. Oil penetration on the back is less than 50% of the area.

[0182] 1: Oil penetration on the inside. Oil penetration on the back is 50% or more and less than 100% of the area.

[0183] 0: Oil penetration on the entire back.

[0184] [Example 1] Paraffin (melting point 69.8°C) 2 g, polyoxyethylene alkyl ether (alkyl carbon atom number 6 to 16, HLB: 7) 0.2 g, and water 17.8 g were mixed to obtain an aqueous dispersion. After the aqueous dispersion was heated to 85°C, it was treated with an ultrasonic homogenizer for 20 minutes, and thus an aqueous-dispersible oil repellent was obtained. The obtained aqueous-dispersible oil repellent showed the following properties.

[0185] Median particle diameter D50: 0.8 μm Volume presence ratio of particles of 100 μm or more: 0% Volume presence ratio of particles of 10 μm or more: 12% Charge density: 20 μeq / g A water-dispersible oil repellent was added to an aqueous pulp slurry having a concentration of 0.5 wt% in a ratio of 5 wt% relative to the pulp, converted to solid content, to prepare a pulp composition. The pulp containing water-dispersible oil repellent was added to an automatic molding machine to produce a pulp molded article.

[0186] The pulp molded article was subjected to an oil repellency test, and the result was 4. The result is shown in Table 1.

[0187] [Example 2] A microcrystalline wax (melting point 82.9°C) 2 g, a polyoxyethylene alkyl ether (alkyl carbon number 6 to 16, HLB: 7) 0.2 g, and water 17.8 g were mixed to obtain a water dispersion. The water dispersion was warmed to 95°C, and then treated with an ultrasonic homogenizer for 20 minutes to obtain a water-dispersible oil repellent. The obtained water-dispersible oil repellent showed the following properties.

[0188] Median particle diameter D50: 0.85 μm Volume presence ratio of particles of 100 μm or more: 0% Volume presence ratio of particles of 10 μm or more: 18% Charge density: 15 μeq / g

[0189] A pulp composition was prepared using the obtained water-dispersible oil repellent, in the same manner as in Example 1, to produce a pulp molded article.

[0190] The pulp molded article was subjected to an oil repellency test, and the result was 4. The result is shown in Table 1.

[0191] [Example 3] A paraffin wax (melting point 69.8°C) 2 g, benzalkonium chloride 0.18 g, and water 17.8 g were mixed to obtain a water dispersion. The water dispersion was warmed to 85°C, and then treated with an ultrasonic homogenizer for 20 minutes to obtain a water-dispersible oil repellent. The obtained water-dispersible oil repellent showed the following properties.

[0192] Median particle diameter D50: 0.75 μm Volume presence ratio of particles of 100 μm or more: 0% Volume presence ratio of particles of 10 μm or more: 8% Charge density: 75 μeq / g A pulp composition was prepared using the obtained water-dispersible oil repellent, in the same manner as in Example 1, to produce a pulp molded article.

[0193] The pulp molded article was subjected to an oil repellency test, and the result was 4. The result is shown in Table 1.

[0194] [Example 4] The microcrystalline wax (melting point 79°C) was ground to 1 mm or less using a mortar, and dry grinding treatment was performed using an air jet mill pulverizer to obtain a powder of the microcrystalline wax. The particle diameter of the powder of the microcrystalline wax was measured using a laser diffraction / scattering device, and as a result, the median particle diameter D50 was 0.99 μm.

[0195] The powder of the microcrystalline wax 2 g, polyoxyethylene alkyl ether (alkyl carbon atom number 6 to 16, HLB: 7) 0.2 g, and water 17.8 g were mixed to obtain an oil repellent of the water dispersion type. The obtained oil repellent of the water dispersion type showed the following properties.

[0196] Median particle diameter D50: 0.95 μm Volume presence ratio of particles of 100 μm or more: 0% Volume presence ratio of particles of 10 μm or more: 25% Charge density: 2 μeq / g Using the obtained oil repellent of the water dispersion type, a pulp composition was prepared in the same manner as in Example 1, and a pulp molded article was produced.

[0197] The pulp molded article was subjected to an oil repellency test, and the result was 4 points. The results are shown in Table 1.

[0198] [Example 5] The paraffin wax 2 g, cationic starch 0.05 g, rosin acid derivative (rosin-based sizing agent) 0.04 g, formic acid 0.04 g, acetic acid 0.04 g, and water 7.83 g were mixed, warmed to 95°C, and then treated for 20 minutes using an ultrasonic homogenizer to obtain an oil repellent of the water dispersion type. The obtained oil repellent of the water dispersion type showed the following properties.

[0199] Median particle diameter D50: 0.6 μm Volume presence ratio of particles of 100 μm or more: 0% Volume presence ratio of particles of 10 μm or more: 0.2% Charge density: 14 μeq / g Using the obtained oil repellent of the water dispersion type, a pulp composition was prepared in the same manner as in Example 1, and a pulp molded article was produced.

[0200] The pulp molded article was subjected to an oil repellency test, and the result was 4 points. The results are shown in Table 1.

[0201] Furthermore, the average particle diameter of the particles obtained by removing the liquid medium from the oil repellent of the water dispersion type was 0.45 μm.

[0202] [Example 6] Paraffin wax 2 g, cationic starch 0.10 g, rosin acid derivative (rosin-based sizing agent) 0.04 g, formic acid 0.02 g, acetic acid 0.02 g, and water 7.87 g were mixed, warmed to 95°C, and then treated with an ultrasonic homogenizer for 20 minutes, thereby obtaining an oil-resistant water dispersion. The obtained oil-resistant water dispersion showed the following properties.

[0203] Median particle diameter D50: 0.22 μm Volume presence ratio of particles of 100 μm or more: 0% Volume presence ratio of particles of 10 μm or more: 0.1% Charge density: 39 μeq / g Using the obtained oil-resistant water dispersion, a pulp composition was prepared and a pulp molded product was produced in the same manner as in Example 1.

[0204] The oil resistance test was performed on the pulp molded product, and the result was 4 points. The result is shown in Table 1.

[0205] Further, the average particle diameter of the particles obtained by removing the liquid medium from the oil-resistant water dispersion was 0.84 μm.

[0206] [Example 7] Paraffin wax 2 g, sodium oleate 0.1 g, and water 8 g were mixed, warmed to 95°C, and then treated with an ultrasonic homogenizer for 20 minutes, thereby obtaining an oil-resistant water dispersion. The obtained oil-resistant water dispersion showed the following properties.

[0207] Median particle diameter D50: 0.45 μm Volume presence ratio of particles of 100 μm or more: 0% Volume presence ratio of particles of 10 μm or more: 0% Charge density: -143 μeq / g Using the obtained oil-resistant water dispersion, a pulp composition was prepared and a pulp molded product was produced in the same manner as in Example 1.

[0208] The oil resistance test was performed on the pulp molded product, and the result was 4 points. The result is shown in Table 1.

[0209] Further, the average particle diameter of the particles obtained by removing the liquid medium from the oil-resistant water dispersion was 0.45 μm.

[0210] [Example 8] Paraffin wax 2 g, sodium dodecyl sulfate 0.2 g, and water 8 g were mixed, warmed to 95°C, and then treated with an ultrasonic homogenizer for 20 minutes, thereby obtaining an oil-resistant water dispersion. The obtained oil-resistant water dispersion showed the following properties.

[0211] Median particle diameter D50: 0.8 μm Volume presence ratio of particles of 100 μm or more: 0% Volume presence ratio of particles of 10 μm or more: 12% Charge density: -351 μeq / g Using the obtained water-dispersible oil repellent, a pulp composition was prepared and a pulp molded article was produced in the same manner as in Example 1.

[0212] The oil repellency test was performed on the pulp molded article, and the result was 4. The result is shown in Table 1.

[0213] Further, the average particle diameter of the particles obtained by removing the liquid medium from the oil repellent was 0.54 μm.

[0214] [Comparative Example 1] Paraffin wax 2 g, polyoxyethylene alkyl ether (alkyl carbon atom number 6 to 16, HLB: 7) 0.2 g, and water 17.8 g were mixed, warmed to 90°C, and then cooled with stirring by a magnetic stirrer, whereby a water-dispersible oil repellent was obtained. The obtained water-dispersible oil repellent showed the following properties.

[0215] Median particle diameter D50: 88 μm Volume presence ratio of particles of 100 μm or more: 35% Volume presence ratio of particles of 10 μm or more: 98% Using the obtained water-dispersible oil repellent, a pulp composition was prepared and a pulp molded article was produced in the same manner as in Example 1.

[0216] The oil repellency test was performed on the pulp molded article, and the result was 2. The result is shown in Table 1.

[0217] [Table 1]

Claims

1. A wax, characterized in that: It consists of wax particles used in oil-resistant agents for pulp. The volumetric median particle size D50 of the wax is between 0.01 μm and 1 μm.

2. The wax as described in claim 1, characterized in that: It is a petroleum wax.

3. The wax as described in claim 1 or 2, characterized in that: It is selected from at least one of paraffin wax and microcrystalline wax.

4. The wax according to any one of claims 1 to 3, characterized in that: It is used for internal addition.

5. The wax according to any one of claims 1 to 4, characterized in that: The wax is at least one selected from paraffin wax and microcrystalline wax. For internal addition. The median particle size D50 is above 0.1 μm and below 1 μm.

6. An oil-resistant agent for pulp, characterized in that: The wax comprises any one of claims 1 to 5.

7. An oil-resistant agent for pulp, which is a water-dispersible composition, characterized in that: Contains wax and dispersant. The volume median particle size D50 of the oil-resistant agent for pulp is above 0.01 μm and below 1 μm.

8. The oil-resistant agent for pulp as described in claim 7, characterized in that: The particles obtained by removing the liquid medium through natural drying at room temperature have an average particle size of ≥0.01μm and ≤1μm, as observed by scanning electron microscopy.

9. The oil-resistant agent for pulp as described in claim 7 or 8, characterized in that: The wax is petroleum wax.

10. The oil-resistant agent for pulp according to any one of claims 7 to 9, characterized in that: The wax is at least one selected from paraffin wax and microcrystalline wax.

11. The oil-resistant agent for pulp according to any one of claims 7 to 10, characterized in that: The charge density is between -600 μeq / g and 100 μeq / g.

12. The oil-resistant agent for pulp according to any one of claims 7 to 11, characterized in that: It contains organic or inorganic acids.

13. The oil-resistant agent for pulp according to any one of claims 7 to 12, characterized in that: The wax is at least one selected from paraffin wax and microcrystalline wax. The dispersant is at least one selected from nonionic dispersants, anionic dispersants, and cationic dispersants. The pulp additives contain organic acids. The amount of the dispersant is 1 part by weight or less and 50 parts by weight relative to 100 parts by weight of the wax. The volumetric median particle size D50 is between 0.1 μm and 1 μm. The volume fraction of particles larger than 100 μm is less than 20%. The volume fraction of particles larger than 10 μm is less than 40%. The charge density is between -400 μeq / g and 400 μeq / g.

14. A method for manufacturing pulp products, characterized in that, include: The process of treating a pulp substrate with the oil-resistant agent for pulp according to any one of claims 6 to 13.

15. A pulp product, characterized in that: It is a pulp product obtained by treating the pulp with an oil-resistant agent according to any one of claims 6 to 13.

16. The pulp product as described in claim 15, characterized in that: It is a pulp molded product for food contact use.

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