Oil-resistant agent for pulp

Abstract

Provided is a novel oil-resistant agent for pulp, the oil-resistant agent containing a hydrocarbon group-containing polymer, wherein: the hydrocarbon group-containing polymer has a repeating unit derived from a monomer (a1); the monomer (a1) is a hydrocarbon group-containing monomer having a hydrocarbon group, which has 6-40 carbon atoms, and an NH group-containing group; and the amount of the repeating unit derived from the monomer (a1) is more than 90 wt% with respect to the amount of the polymer. With the oil-resistant agent for pulp, it is possible to impart oil resistance to a base material (in particular, a pulp base material).

Description

Oil-resistant agent for pulp

[0001] The present disclosure relates to oil repellents, particularly to oil-resistant agents for pulp.

[0002] Patent Document 1 discloses an oil-resistant agent containing a hydrocarbon group-containing polymer having repeating units formed from a monomer having a hydrocarbon group having 1 to 40 carbon atoms and an NH group-containing group in an amount of 80% by weight or more based on the polymer.

[0003] Japanese Patent Application Laid-Open No. 2023-10656

[0004] In Patent Document 2, the case where the ratio of the hydrocarbon group-containing monomer is particularly high is not examined.

[0005] An object of the present disclosure is to provide a novel oil-proofing agent that can impart oil resistance to a substrate (particularly a pulp substrate).

[0006] The present disclosure includes the following aspects: [Item 1] An oil-proofing agent for pulp comprising a hydrocarbon group-containing polymer, wherein the hydrocarbon group-containing polymer has repeating units derived from a monomer (a1), the monomer (a1) is a hydrocarbon group-containing monomer having from 6 to 40 carbon atoms and having a hydrocarbon group and an NH group-containing group, and the amount of repeating units derived from the monomer (a1) is more than 90 wt % of the polymer. [Item 2] The oil-proofing agent for pulp according to Item 1, wherein the hydrocarbon group-containing polymer does not contain fluorine atoms. [Item 3] The monomer (a1) is a hydrocarbon group-containing polymer represented by the formula (a1): CH2=C(-X ａ１ )-C(=O)-Y ａ１１ -Z (-Y ａ１２ -R ａ１ ) ｎ [In the formula, R ａ１ are each independently a hydrocarbon group having 6 to 40 carbon atoms, ａ１ is a hydrogen atom, a monovalent organic group or a halogen atom, ａ１１ is —O— or —NH—, and Y ａ１２ are each independently a direct bond, or —O—, —C(═O)—, —S(═O) ２ -, -NH- or -CH ２-, Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and n is 1 or 2. [Item 4] The oil-proofing agent for pulp according to any one of Items 1 to 3, wherein the amount of repeating units derived from the monomer (a1) is more than 97% by weight based on the polymer. [Item 5] The oil-proofing agent for pulp according to any one of Items 1 to 4, wherein the amount of repeating units derived from the monomer (b) is 0% by weight or more and less than 7% by weight based on the polymer, and the monomer (b) is a hydrophilic monomer having an oxyalkylene-containing group as the hydrophilic group. [Item 6] The oil-proofing agent for pulp according to any one of Items 1 to 5, wherein the amount of repeating units derived from the monomer (c) is 0% by weight or more and less than 3% by weight based on the polymer, and the monomer (c) is an ionic group-containing monomer. [Item 7] The oil-proofing agent for pulp according to any one of Items 1 to 6, wherein the hydrocarbon group-containing polymer is a polymer obtained by emulsion polymerization. [Item 8] The oil-proofing agent for pulp according to any one of Items 1 to 7, which comprises a dispersant. [Item 9] The oil-proofing agent for pulp according to any one of Items 1 to 8, which comprises an anionic dispersant. [Item 10] The oil-proofing agent for pulp according to any one of Items 1 to 9, which comprises a lignin compound. [Item 11] The oil-proofing agent for pulp according to any one of Items 1 to 10, which comprises an aqueous medium. [Item 12] Y ａ１２is -NH-C(=O)-, -C(=O)-NH-, -O-C(=O)-NH-, -NH-C(=O)-O-, or -NH-C(=O)-NH-. [Item 13] A pulp composition comprising a pulp base material and the oil-proofing agent for pulp according to any one of Items 1 to 12. [Item 14] The pulp composition according to Item 13, comprising at least one pulp additive selected from the group consisting of a sizing agent, a strength agent, and a fixing agent. [Item 15] An oil-resistant pulp product, in which the hydrocarbon group-containing polymer in the oil-proofing agent for pulp according to any one of Items 1 to 12 is adhered to a pulp base material. [Item 16] The oil-resistant pulp product according to Item 15, which is a molded pulp product. [Item 17] The oil-resistant pulp product according to Item 15 or 16, which is a food packaging material or a food container. [Item 18] A method for producing an oil-resistant pulp product, comprising a step of treating a pulp base material by external addition or internal addition with the oil-proofing agent according to any one of Items 1 to 12. [Item 19] A method for producing an oil-resistant pulp product according to Item 18, comprising filling a mold with the oil-proofing agent and a pulp slurry, and allowing a liquid medium to permeate out of the mold to form pulp.

[0007] According to the present disclosure, oil resistance can be imparted to a substrate (particularly a pulp substrate).

[0008] <Definition of Terms> As used herein, an "n-valent group" refers to a group having n bonds, i.e., a group that forms n bonds. Furthermore, an "n-valent organic group" refers to an n-valent group containing carbon. Such an organic group is not particularly limited, but may be a hydrocarbon group or a derivative thereof. A hydrocarbon group derivative refers to a group having one or more of N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, halogen, etc. at the end or molecular chain of the hydrocarbon group.

[0009] As used herein, the term "hydrocarbon group" refers to a group containing carbon and hydrogen, which is a group obtained by removing a hydrogen atom from a hydrocarbon. Such hydrocarbon groups include, but are not limited to, C １－２０Examples of hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. The hydrocarbon group may contain one or more ring structures. The hydrocarbon group may be substituted with one or more substituents, if explicitly stated.

[0010] In this specification, when a term (symbol) that may appear multiple times in a chemical structure is defined, that definition applies independently at each occurrence, unless otherwise stated, regardless of whether "independently at each occurrence," "independently of each other," "independently of each other," or similar expressions are explicitly stated.

[0011] The chemical structures described herein should be understood not to encompass chemical structures that would be recognized by those skilled in the art as chemically impossible or extremely unstable.

[0012] <Repellent (Oil-Resistant Agent)> The repellent agent in the present disclosure adheres to a substrate (particularly a pulp substrate) and can impart liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or stain resistance, to the substrate, and can also function as a water-resistant agent, oil-resistant agent, water repellent, oil repellent, and / or stain resistance. The repellent agent in the present disclosure is particularly suitable as an oil-resistant agent that imparts oil resistance to a substrate (particularly a pulp substrate).

[0013] Because the adhesion of chemicals to the surface of a pulp substrate is a reversible reaction, it is believed that the application of shear makes it difficult for adhesion to be maintained. In particular, the continuous application of shear during prolonged stirring is thought to be detrimental to chemical fixation. Despite this, the inventors have unexpectedly discovered that by using the repellent of the present disclosure, even when the pulp slurry after addition of the repellent is stirred for a long period of time (e.g., 30 minutes or more), the product (e.g., pulp mold) exhibits excellent high-temperature oil resistance.

[0014] The repellent of the present disclosure contains, as an active ingredient, a hydrocarbon group-containing polymer, which is a liquid repellent compound described below. The hydrocarbon group-containing polymer may be used as a repellent by itself, or may be used as a repellent in combination with other ingredients.

[0015] The repellent agent in the present disclosure may not contain any compound selected from the group consisting of a compound having a fluoroalkyl group having 8 or more carbon atoms, a compound having a perfluoroalkyl group having 8 or more carbon atoms, a compound having a fluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group, a compound having a fluoroalkyl group, and a compound having a fluorine atom. The repellent agent in the present disclosure can impart liquid repellency to a substrate even if it does not contain these fluorine compounds.

[0016] The volumetric abundance ratio of particles of 100 μm or larger in the repellent agent of the present disclosure, as measured by a laser diffraction scattering method, may be 0.1% or larger, 0.3% or larger, 0.5% or larger, 1% or larger, 1.5% or larger, 3% or larger, 4% or larger, 5% or larger, or 10% or larger, or may be 50% or smaller, 30% or smaller, 20% or smaller, 15% or smaller, 10% or smaller, 5% or smaller, 3% or smaller, or 1.5% or smaller, preferably 20% or smaller, and more preferably 5% or smaller. The method for achieving the volumetric abundance ratio of such particles within the above range is not limited, and may involve, for example, micronizing the particles in the raw material and / or dispersion using a grinder, homogenizer, or the like.

[0017] The volumetric abundance ratio of particles of 10 μm or larger in the composition of the present disclosure, as measured by a laser diffraction scattering method, may be 0.1% or larger, 0.3% or larger, 0.5% or larger, 1% or larger, 1.5% or larger, 3% or larger, 4% or larger, 5% or larger, or 10% or larger, or may be 50% or smaller, 30% or smaller, 20% or smaller, 15% or smaller, 10% or smaller, 5% or smaller, 3% or smaller, or 1.5% or smaller, preferably 30% or smaller, more preferably 15% or smaller. The method for achieving the volumetric abundance ratio of such particles within the above range is not limited, and may be, for example, by micronizing the particles in the raw material and / or dispersion using a grinder, homogenizer, or the like.

[0018] The volume median diameter of the repellent agent of the present disclosure, as measured by a laser diffraction scattering method, may be 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.2 μm or more, 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, or 0.6 μm or more, or may be 10 μm or less, 5 μm or less, 3 μm or less, 1 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, 0.3 μm or less, or 0.2 μm or less, preferably 1 μm or less, and in one embodiment, 0.01 μm or more and 1 μm or less. In the present disclosure, the volume median diameter refers to the median diameter (D50) in a volume-based particle size distribution measured by a laser diffraction scattering method.

[0019] The average particle size, as determined from a scanning electron microscope image of particles obtained by removing the liquid medium from a water-dispersed composition of the present disclosure (e.g., an oil-resistant agent for pulp) by natural drying at room temperature, may be 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.2 μm or more, 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, or 0.6 μm or more, or 10 μm or less, 5 μm or less, 3 μm or less, 1 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, 0.3 μm or less, or 0.2 μm or less, preferably 1 μm or less. To achieve a particle size within the above range, for example, the particles in the raw material and / or dispersion may be micronized using a grinder, homogenizer, or the like. The room temperature is 20°C to 30°C, particularly 25°C.

[0020] The ionic charge density in the repellent of the present disclosure may be -1000 μeq / g or more, -800 μeq / g or more, -600 μeq / g or more, -500 μeq / g or more, -400 μeq / g or more, -250 μeq / g or more, -100 μeq / g or more, -50 μeq / g or more, -25 μeq / g or more, 0 μeq / g or more, 1 μeq / g or more, 25 μeq / g or more, 50 μeq / g or more, 100 μeq / g or more, 200 μeq / g or more, preferably -600 μeq / g or more, for example, -400 μeq / g or more, -200 μeq / g or more, -50 μeq / g or more, or 5000 μeq / g or less. , 2500 μeq / g or less, 1000 μeq / g or less, 750 μeq / g or less, 600 μeq / g or less, 500 μeq / g or less, 400 μeq / g or less, 350 μeq / g or less, 300 μeq / g or less, 200 μeq / g or less, 100 μeq / g or less, or 50 μeq / g or less, preferably 1000 μeq / g or less, more preferably 500 μeq / g or less, for example 300 μeq / g or less, particularly 100 μeq / g or less, and in one preferred embodiment, it may be -1500 μeq / g or more and 1500 μeq / g or less, particularly -1500 μeq / g or more and 0 μeq / g or less.

[0021] A sample liquid with a solid content of 0.1 g / L is subjected to anion demand measurement using a particle charge meter (MUTEK PCD-06 manufactured by BTG) using a 1 / 1000 N potassium polyvinyl sulfonate solution, and the ionic charge density (cationic charge density) is calculated using the following formula (1). Alternatively, the cation demand is measured in the same manner using a polydiallyldimethylammonium chloride solution instead of potassium polyvinyl sulfonate, and the ionic charge density (anionic charge density) is calculated using the following formula (1). Ionic charge density (μeq / g) = A / B (1) A: cation demand or anion demand (μeq / L) B: sample liquid concentration (g / L)

[0022] [Hydrocarbon Group-Containing Polymer] The repellent agent of the present disclosure includes a hydrocarbon group-containing polymer. The hydrocarbon group-containing polymer of the present disclosure adheres to a substrate (particularly a pulp substrate) and imparts liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or stain resistance, particularly oil resistance, to the substrate.

[0023] The hydrocarbon group-containing polymer is a polymer obtained by polymerizing a vinyl monomer and exhibits liquid repellency. Here, the vinyl monomer may be any compound having a polymerizable carbon-carbon double bond (ethylenically unsaturated double bond) (>C=C<), and may be a monomer containing a vinyl group, a vinylene group, a vinylidene group, an acryloyl group, a methacryloyl group, or a derivative group thereof.

[0024] [Characteristics, etc.] The characteristics, etc. that the hydrocarbon group-containing polymer may have are shown below.

[0025] The HD (n-hexadecane) contact angle of the hydrocarbon group-containing polymer may be 10° or more, 20° or more, 25° or more, 30° or more, 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 60° or more, or 65° or more, preferably 25° or more, more preferably 30° or more, and may be 100° or less, 90° or less, or 75° or less. When the hydrocarbon group-containing polymer has an HD contact angle equal to or greater than the above lower limit, it can impart good liquid repellency (particularly oil repellency) to the substrate. The HD contact angle is the static contact angle of the hydrocarbon group-containing polymer with a spin-coated film, and is obtained by dropping 2 μL of HD onto the spin-coated film at room temperature (25° C.) and measuring the contact angle one second after the drop has landed.

[0026] The water contact angle of the hydrocarbon group-containing polymer may be 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 65° or more, 75° or more, 85° or more, 90° or more, or 100° or more, and may be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. When the hydrocarbon group-containing polymer has a water contact angle equal to or greater than the above lower limit, it can impart good liquid repellency (particularly water repellency) to the substrate. The water contact angle is the static contact angle of the hydrocarbon group-containing polymer with a spin-coated film, and is obtained by dropping 2 μL of water onto the spin-coated film at room temperature (25° C.) and measuring the contact angle one second after the drop hits the film.

[0027] The hydrocarbon group-containing polymer is preferably a biobased compound containing carbon of biobased origin. The biobased content is measured in accordance with ASTM D6866. The biobased content may be 20% or more, preferably 30% or more, more preferably 50% or more, even more preferably 60% or more, even more preferably 70% or more, and most preferably 80% or more or 90% or more, for example, 100%. A high biobased content means that the amount of fossil resource-based materials, such as petroleum, used is small. From this perspective, the higher the biobased content of the hydrocarbon group-containing polymer, the better.

[0028] The hydrocarbon group-containing polymer preferably has a biodegradability of 5% or more after 180 days. Higher biodegradability is preferable because it reduces the environmental impact. The hydrocarbon group-containing polymer may have a biodegradability of, for example, 10% or more, 20% or more, 30% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more after 180 days, preferably 30% or more, more preferably 50% or more, even more preferably 70% or more, and most preferably 80% or more after 60 days. The hydrocarbon group-containing polymer preferably has a biodegradability of 5% or more after 60 days. Higher biodegradability is preferable because it reduces the environmental impact. The hydrocarbon group-containing polymer may have a biodegradability of, for example, 10% or more, 15% or more, 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, or 45% or more after 60 days, preferably 10% or more, more preferably 30% or more. Such biodegradability may be biodegradability as defined in JIS K 6953-1 or ASTM D6400.

[0029] The melting point of the hydrocarbon group-containing polymer may be 30°C or higher, 40°C or higher, 60°C or higher, 80°C or higher, 100°C or higher, or 120°C or higher, preferably 40°C or higher, and may be 250°C or lower, 225°C or lower, 200°C or lower, 150°C or lower, 130°C or lower, 120°C or lower, 110°C or lower, 100°C or lower, 80°C or lower, or 50°C or lower.

[0030] [Structure etc.] The hydrocarbon group-containing polymer in the present disclosure does not necessarily have any group selected from the group consisting of a fluoroalkyl group having 8 or more carbon atoms, a perfluoroalkyl group having 8 or more carbon atoms, a fluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group, a fluoroalkyl group, and a fluorine atom. Even if the hydrocarbon group-containing polymer does not contain these fluorine-containing groups, it can impart liquid repellency to a substrate.

[0031] The weight average molecular weight of the hydrocarbon group-containing polymer may be 3,000 or more, 5,000 or more, 10,000 or more, 30,000 or more, 100,000 or more, 300,000 or more, or 500,000 or more, and may be 5,000,000 or less, 3,000,000 or less, 1,000,000 or less, 750,000 or less, 500,000 or less, 300,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, or 5,000 or less. The weight average molecular weight may be a polystyrene-equivalent molecular weight measured by GPC.

[0032] (a) Hydrocarbon Group-Containing Monomer The hydrocarbon group-containing polymer may have a repeating unit derived from a hydrocarbon group-containing monomer (a). The monomer (a) has one ethylenically unsaturated double bond and a hydrocarbon group having from 6 to 40 carbon atoms.

[0033] The monomer (a) preferably has a (meth)acrylic group as the group having an ethylenically unsaturated double bond, and may have, for example, a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond.

[0034] Monomer (a) has a hydrocarbon group having 6 to 40 carbon atoms. Here, the hydrocarbon group is a monovalent group. The hydrocarbon group of monomer (a) may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group is branched or linear, and more preferably linear. The hydrocarbon group may be saturated or unsaturated. The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group (alkyl group). The number of carbon atoms in the hydrocarbon group may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, preferably 10 or more, 12 or more, 14 or more, or 16 or more, and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, and preferably 30 or less, 25 or less, or 20 or less.

[0035] The monomer (a) having a hydrocarbon group having 6 to 40 carbon atoms is represented by the formula: CH2=C(-X ａ )-C(=O)-Y ａ (R ａ ) ｋ [In the formula, R ａ are each independently a hydrocarbon group having 6 to 40 carbon atoms, ａ is a hydrogen atom, a monovalent organic group or a halogen atom, ａ represents a divalent to tetravalent hydrocarbon group having one carbon atom (particularly, —CH ２ -, -CH(-) ２ ), -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２ - or -NH-, and k is an integer of 1 to 3.

[0036] X ａ may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. ａ Examples of X are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, and a cyano group. ａis preferably a hydrogen atom, a methyl group, or a chlorine atom. ａ is particularly preferably a hydrogen atom.

[0037] Y ａ is a divalent to tetravalent group. ａ is preferably a divalent group. ａ represents a hydrocarbon group having one carbon atom, -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２ It is preferable that Y is a group constituted by at least one selected from - and -NH-. ａ is preferably not a hydrocarbon group. Examples of hydrocarbon groups having one carbon atom include -CH ２ -, -CH(-) ２ or -C(-) ３ The hydrocarbon group having one carbon atom is repeated, and -(CH ２ ) m A hydrocarbon group having two or more carbon atoms may be formed, such as Y - (where m is an integer of 1 to 5). ａ may have an NH group.

[0038] Y ａ -Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-R'-, -Y'-R'-Y'- , -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O)-Y'-, -Y'-R'-Y'-C(=O)-Y'-, or -Y'-R'-Y'-R'- [In the formula, Y' is a direct bond, -O-, -NH- or -S(=O) ２ - and R' is -(CH ２ ) m - (m is an integer of 1 to 5) or -C ６ H ４ -(phenylene group).

[0039] Y ａ Specific examples of are -O-, -NH-, -OC(=O)-, -C(=O)-NH-, -NH-C(=O)-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C ６ H ４-、-O-(CH ２ ) m -O-、-NH-(CH ２ ) m -NH-、-O-(CH ２ ) m -NH-、-NH-(CH ２ ) m -O-、-O-(CH ２ ) m -O-C(=O)-、-O-(CH ２ ) m -C(=O)-O-,-NH-(CH ２ ) m -O-C(=O)-,-NH-(CH ２ ) m -C(=O)-O-、-O-(CH ２ ) m -O-C(=O)-NH-,-O-(CH ２ ) m -NH-C(=O)-O-,-O-(CH ２ ) m -C(=O)-NH-,-O-(CH ２ ) m -NH-C(=O)-,-O-(CH ２ ) m -NH-C(=O)-NH-,-O-(CH ２ ) m -O-C ６ H ４ -、-O-(CH ２ ) m -NH-S(=O) ２ -、-O-(CH ２ ) m -S(=O) ２ -NH-、-NH-(CH ２ ) m -O-C(=O)-NH-,-NH-(CH ２ ) m -NH-C(=O)-O-,-NH-(CH ２ ) m -C(=O)-NH-,-NH-(CH ２ ) m -NH-C(=O)-,-NH-(CH ２ ) m -NH-C(=O)-NH-,-NH-(CH ２ ) m-O-C ６ H ４ -, -NH-(CH ２ ) m -NH-C ６ H ４ -, -NH-(CH ２ ) m -NH-S(=O) ２ -, or -NH-(CH ２ ) m -S(=O) ２ -NH-, wherein m is 1 to 5, particularly 2 or 4.

[0040] Y ａ is -O-, -NH-, -O-(CH ２ ) m -O-C(=O)-, -O-(CH ２ ) m -NH-C(=O)-, -O-(CH ２ ) m -OC(=O)-NH-, -O-(CH ２ ) m -NH-C(=O)-O-, -O-(CH ２ ) m -NH-C(=O)-NH-, -O-(CH ２ ) m -NH-S(=O) ２ -, -O-(CH ２ ) m -S(=O) ２ -NH-, -NH-(CH ２ ) m -NH-S(=O) ２ -, or -NH-(CH ２ ) m -S(=O) ２ -NH- [wherein m is an integer of 1 to 5, particularly 2 or 4] is preferred. ａ is -O- or -O-(CH ２ ) m —NH—C(═O)—, particularly —O—(CH ２ ) m It is more preferably —NH—C(═O)—.

[0041] R ａare each independently a hydrocarbon group having from 6 to 40 carbon atoms, and are preferably a linear or branched hydrocarbon group. The hydrocarbon group may particularly be a linear hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, and especially an alkyl group. The hydrocarbon group preferably has 12 to 30 carbon atoms, for example, 12 to 18 carbon atoms, 16 to 26 or 15 to 26, particularly 18 to 22 or 17 to 22 carbon atoms.

[0042] Specific examples of the monomer (a) include the monomer (a1) and the monomer (a2) described below.

[0043] Monomer (a1) Monomer (a1) is a monomer different from monomer (a2), and is particularly a monomer having a hydrocarbon group having 6 to 40 carbon atoms and an NH group-containing group.

[0044] The monomer (a1) may contain an amide group, a urea group, a urethane group, or a sulfonamide group. The NH group-containing group may be an amide group, a urea group, a urethane group, or a sulfonamide group. The hydrocarbon-based monomer may be a combination of a hydrocarbon-based monomer having an amide group, a urea group, a urethane group, or a sulfonamide group and a hydrocarbon-based monomer not having an amide group, a urea group, a urethane group, or a sulfonamide group. When the monomer (a1) contains such a group, the effects of the present disclosure can be effectively achieved.

[0045] The monomer (a1) is —O—, —C(═O)—, —S(═O) ２ -, -NH- or -CH ２ - is a (meth)acrylate or (meth)acrylamide having at least one group selected from the group consisting of:

[0046] The monomer (a1) has the formula: CH2=C(-X ａ１ )-C(=O)-Y ａ１１ -Z (-Y ａ１２ -R ａ１ ) ｎ [In the formula, R ａ１ are each independently a hydrocarbon group having 6 to 40 carbon atoms, ａ１ is a hydrogen atom, a monovalent organic group or a halogen atom,ａ１１ is —O— or —NH—, and Y ａ１２ are each independently a direct bond, or —O—, —C(═O)—, —S(═O) ２ -, -NH- or -CH ２ -, Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and n is 1 or 2. ａ１２ and / or Z may not be a direct bond. ａ１２ and Z may not be a direct bond at the same time.

[0047] R ａ１ is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. ａ１ In the formula (I), the hydrocarbon group preferably has 12 to 30 carbon atoms, for example, 16 to 26 or 15 to 26, and particularly preferably 18 to 22 or 17 to 22 carbon atoms.

[0048] X ａ１ may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group, and is preferably a hydrogen atom, a methyl group, or a chlorine atom.

[0049] Y ａ１２ represents -Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-R'-, -Y'-R'-Y'-, -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O)-Y'-, -Y'-R'-Y'-C(=O)-Y'-, or -Y'-R'-Y'-R'-, wherein each Y' independently represents a direct bond, -O-, -NH-, or -S(=O) ２ - and R' is -(CH ２ ) ｍ - (m is an integer of 1 to 5), a linear hydrocarbon group having an unsaturated bond of 1 to 5 carbon atoms, a hydrocarbon group having a branched structure of 1 to 5 carbon atoms, or -(CH ２ ) ｌ -C ６ H ４ -(CH ２ ) ｌ- (each l is independently an integer of 0 to 5; -C ６ H ４ - is a phenylene group.

[0050] Especially Y ａ１２ may have an NH group.

[0051] Y ａ１２ Specific examples include direct bond, -O-, -NH-, -OC(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S(=O) ２ -, -S(=O) ２ -NH-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -OC ６ H ４ -, -NH-C ６ H ４ -, -O-(CH ２ ) m -O-, -NH-(CH ２ ) m -NH-, -O-(CH ２ ) m -NH-, -NH-(CH ２ ) m -O-, -O-(CH ２ ) m -O-C(=O)-, -O-(CH ２ ) m -C(=O)-O-, -NH-(CH ２ ) m -OC(=O)-, -NH-(CH ２ ) m -C(=O)-O-, -O-(CH ２ ) m -OC(=O)-NH-, -O-(CH ２ ) m -NH-C(=O)-O-, -O-(CH ２ ) m -C(=O)-NH-, -O-(CH ２ ) m -NH-C(=O)-, -O-(CH ２ ) m -NH-C(=O)-NH-, -O-(CH ２ ) m -O-C ６ H４ -, -NH-(CH ２ ) m -OC(=O)-NH-, -NH-(CH ２ ) m -NH-C(=O)-O-, -NH-(CH ２ ) m -C(=O)-NH-, -NH-(CH ２ ) m -NH-C(=O)-, -NH-(CH ２ ) m -NH-C(=O)-NH-, -NH-(CH ２ ) m -O-C ６ H ４ -, -NH-(CH ２ ) m -NH-C ６ H ４ wherein m is an integer of 1 to 5.

[0052] Y ａ１２ is -O-, -NH-, -O-C(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S(=O) ２ -, -S(=O) ２ -NH-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -OC ６ H ４ - is preferred. ａ１２ is more preferably —NH—C(═O)—, —C(═O)—NH—, —O—C(═O)—NH—, —NH—C(═O)—O— or —NH—C(═O)—NH—. ａ１２ may not be a direct bond.

[0053] Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and may have a linear or branched structure. Z preferably has 2 to 4 carbon atoms, and particularly preferably 2. Specific examples of Z include a direct bond, -CH ２ -, -CH ２ CH ２ -, -CH ２ CH ２ CH ２ -, -CH ２ CH ２CH ２ CH ２ -, -CH ２ CH ２ CH ２ CH ２ CH ２ -, -CH ２ CH(-) ２ , -CH ２ (CH-)CH ２ -, -CH ２ CH ２ CH(-) ２ , -CH ２ CH ２ CH ２ CH ２ CH(-) ２ , -CH ２ CH ２ (CH-)CH ２ -, -CH ２ CH ２ CH ２ CH(-) ２ Z does not have to be a direct bond.

[0054] Monomer (a1) is CH2=C(-X ａ１ )-C(=O)-O-(CH ２ ) m -NH-C(=O)-R ａ１ , C.H. ２ =C(-X ａ１ )-C(=O)-O-(CH ２ ) ｍ -OC(=O)-NH-R ａ１ , C.H. ２ =C(-X ａ１ )-C(=O)-O-(CH ２ ) ｍ -NH-C(=O)-OR ａ１ , C.H. ２ =C(-X ａ１ )-C(=O)-O-(CH ２ ) ｍ -NH-C(=O)-NH-R ａ１ Preferably, R ａ１ and X ａ１ has the same meaning as above.]. The monomer (a1) is CH2=C(-X ａ１ )-C(=O)-O-(CH ２ ) m-NH-C(=O)-R ａ１ It is particularly preferred that:

[0055] Monomer (a1) can be produced by reacting a hydroxyalkyl (meth)acrylate or hydroxyalkyl (meth)acrylamide with a long-chain alkyl isocyanate. Examples of long-chain alkyl isocyanates include lauryl isocyanate, myristyl isocyanate, cetyl isocyanate, stearyl isocyanate, oleyl isocyanate, and behenyl isocyanate. Alternatively, monomer (a1) can be produced by reacting a (meth)acrylate having an isocyanate group in its side chain, such as 2-methacryloyloxyethyl methacrylate, with a long-chain alkylamine or a long-chain alkyl alcohol. Examples of long-chain alkylamines include laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, and behenylamine. Examples of long-chain alkyl alcohols include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and behenyl alcohol.

[0056] Preferred examples of the monomer (a) are as follows: stearyl (meth)acrylate, behenyl (meth)acrylate, stearyl α-chloroacrylate, behenyl α-chloroacrylate; stearyl (meth)acrylamide, behenyl (meth)acrylamide;

[0057]

[0058]

[0059]

[0060]

[0061]

[0062] [In the above formula, n is a number from 6 to 40, and m is a number from 1 to 5.] The compound of the above chemical formula is an acrylic compound having a hydrogen atom at the α-position, but specific examples may be a methacryl compound having a methyl group at the α-position and an α-chloroacrylic compound having a chlorine atom at the α-position.

[0063] The monomer (a1) has the formula: ａ１２ -C(=O)-NH-R ａ１３ -O-R ａ１１ [In the formula, R ａ１１ represents an organic residue having an ethylenically unsaturated polymerizable group, R ａ１２ is a hydrocarbon group having 6 to 40 carbon atoms, R ａ１３ is a hydrocarbon group having 1 to 5 carbon atoms.]

[0064] R ａ１１ is an organic residue having an ethylenically unsaturated polymerizable group, and is not particularly limited as long as it has a polymer carbon-carbon double bond. ａ１１１ =CH ２ , -CHR ａ１１１ =CH ２ , -CH ２ CHR ａ１１１ =CH ２ and the like. ａ１１１ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ａ１１ R may have various organic groups in addition to the ethylenically unsaturated polymerizable group, such as organic groups of chain hydrocarbons, cyclic hydrocarbons, polyoxyalkylene groups, and polysiloxane groups, and these organic groups may be substituted with various substituents. ａ１１ is -C(=O)CR ａ１１１ =CH ２ It is preferable that:

[0065] R ａ１２ is the same as the hydrocarbon group contained in the monomer (a) described above, and is a hydrocarbon group having 6 to 40 carbon atoms, preferably an alkyl group, and examples thereof include chain hydrocarbon groups and cyclic hydrocarbon groups. Among these, a chain hydrocarbon group is preferred, and a linear saturated hydrocarbon group is particularly preferred.ａ１２ The number of carbon atoms is 6 or more and 40 or less, preferably 11 to 27, and particularly preferably 15 to 23.

[0066] R ａ１３ is a hydrocarbon group having 1 to 5 carbon atoms, preferably an alkyl group. The hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched, and may have an unsaturated bond, but is preferably linear. ａ１３ The number of carbon atoms in R is preferably 2 to 4, and particularly preferably 2. ａ１３ is preferably an alkylene group.

[0067] The amide group-containing monomer is R ａ１２ is one type (for example, R ａ１２ is only a compound having 17 carbon atoms), or R ａ１２ A combination of multiple ａ１２ a compound having 17 carbon atoms, and R ａ１２ and a compound having 15 carbon atoms.

[0068] An example of the amide group-containing monomer is carboxylic acid amide alkyl (meth)acrylate.Specific examples of the amide group-containing monomer include palmitic acid amide ethyl (meth)acrylate, stearic acid amide ethyl (meth)acrylate, behenic acid amide ethyl (meth)acrylate, myristate amide ethyl (meth)acrylate, laurate amide ethyl (meth)acrylate, isostearate ethyl amide (meth)acrylate, oleic acid ethyl amide (meth)acrylate, tertiary butylcyclohexyl caproate amide ethyl (meth)acrylate, adamantanecarboxylic acid ethyl amide (meth)acrylate, naphthalenecarboxylic acid amide ethyl (meth)acrylate, anthracenecarboxylic acid amide ethyl (meth)acrylate, palmitic acid amide propyl (meth)acrylate, stearic acid amide propyl (meth)acrylate, palmitic acid amide ethyl vinyl ether, stearic acid amide ethyl vinyl ether, palmitic acid amide ethyl allyl ether, stearic acid amide ethyl allyl ether, and mixtures thereof.

[0069] The amide group-containing monomer is preferably stearamidoethyl (meth)acrylate. The amide group-containing monomer may be a mixture containing stearamidoethyl (meth)acrylate. In the mixture containing stearamidoethyl (meth)acrylate, the amount of stearamidoethyl (meth)acrylate may be, for example, 40 wt% or more, 50 wt% or more, 60 wt% or more, or 70 wt% or more, and 90 wt% or less, 80 wt% or less, or 70 wt% or less, based on the total weight of the amide group-containing monomers. The remaining monomer may be, for example, palmitamidoethyl (meth)acrylate.

[0070] (a2) Monomer Monomer (a2) has the formula: CH2=C(-X ａ２ )-C(=O)-Y ａ２ -R ａ２ [In the formula, R ａ２ is a hydrocarbon group having 6 to 40 carbon atoms, ａ２ is a hydrogen atom, a monovalent organic group or a halogen atom, ａ２ is —O— or —NH—.]

[0071] The monomer (a2) is Y ａ２ a long chain acrylate ester monomer in which Y is —O—; ａ２ is a long chain acrylamide monomer in which R is —NH—. ａ２ is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. ａ２ In the formula (I), the number of carbon atoms in the hydrocarbon group is preferably 12 to 30, for example, 16 to 26, and particularly preferably 18 to 22. ａ２ may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group, and is preferably a hydrogen atom, a methyl group, or a chlorine atom.

[0072] Preferred examples of the long-chain acrylate ester monomer include lauryl (meth)acrylate, stearyl (meth)acrylate, icosyl (meth)acrylate, behenyl (meth)acrylate, stearyl α-chloroacrylate, icosyl α-chloroacrylate, and behenyl α-chloroacrylate. Preferred examples of the long-chain acrylamide monomer include stearyl (meth)acrylamide, icosyl (meth)acrylamide, and behenyl (meth)acrylamide.

[0073] (b) Hydrophilic Group-Containing Monomer The hydrocarbon group-containing polymer may contain a repeating unit derived from a hydrophilic group-containing monomer (b). The monomer (b) is a monomer other than the monomer (a) that has a hydrophilic group.

[0074] The monomer (b) preferably has a (meth)acrylic group as the group having an ethylenically unsaturated double bond, and may have, for example, a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond. The monomer (a) may have one or two groups having an ethylenically unsaturated double bond, but preferably has only one.

[0075] The hydrophilic group is preferably an oxyalkylene-containing group (the alkylene group has 2 to 6 carbon atoms), and particularly preferably an oxyethylene group. In particular, the monomer (b) is preferably an oxyalkylene (meth)acrylate, for example, polyalkylene (or monoalkylene) glycol mono(meth)acrylate and / or polyalkylene (or monoalkylene) glycol di(meth)acrylate, or polyalkylene (or monoalkylene) glycol mono(meth)acrylamide.

[0076] Monomer (b) has the formula: CH ２ =CX ｂ C(=O)-Y ｂ - (R ｂ O) ｎ -A ｂ [In the formula, X ｂ is a hydrogen atom or a methyl group, and Y ｂ is —O— or —NH—, R ｂare each independently an alkylene group having 2 to 6 carbon atoms; ｂ represents a hydrogen atom, an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, or CH ２ =CX ｂ C(═O)—, and n is an integer of 1 to 90.

[0077] Examples of monomer (b) are those of the formula: CH ２ =CX ｂ C(=O)-O-(R ｂ O) ｎ -A ｂｉ (b1) and CH ２ =CX ｂ C(=O)-O-(R ｂ O) ｎ -C(=O)CX ｂ =CH ２ (b2), CH ２ =CX ｂ C(=O)-NH-(R ｂ O) ｎ -A ｂｉ (b3) wherein X ｂ are each independently a hydrogen atom or a methyl group; ｂｉ are each independently a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms; ｂ are each independently an alkylene group having 2 to 6 carbon atoms, and n is an integer of 1 to 90.

[0078] n may be, for example, 1 to 50, particularly 1 to 30, and especially 1 to 15 or 2 to 15. Alternatively, n may be, for example, 1. R ｂ may be a linear or branched alkylene group, for example, a group of the formula -(CH ２ ) ｘ - or - (CH ２ ) ｘ１ -(CH(CH ３ )) ｘ２ - [wherein x1 and x2 are 0 to 6, for example, 2 to 5, and the sum of x1 and x2 is 1 to 6. -(CH ２ ) ｘ１- and - (CH (CH ３ )) ｘ２ The order of - is not limited to the illustrated formula and may be random. ｂ O) n In -, R may be two or more types (for example, two to four types, particularly two types), and -(R ｂ O) n - is, for example, -(R １ O) ｎ１ - and - (R ２ O) ｎ２ - [wherein, R １ and R ２ are different from each other and are alkylene groups having 2 to 6 carbon atoms, n1 and n2 are numbers of 1 or more, and the sum of n1 and n2 is 2 to 90.

[0079] R in formulas (b1), (b2) and (b3) ｂ is particularly preferably an ethylene group, a propylene group or a butylene group, and particularly preferably a butylene group. ｂ R may be a combination of two or more alkylene groups. In this case, it is preferable that at least one of R is an ethylene group, a propylene group, or a butylene group. ｂ Examples of the combination include a combination of an ethylene group / propylene group, a combination of an ethylene group / butylene group, and a combination of a propylene group / butylene group. The monomer (b) may be a mixture of two or more types. In this case, at least one of the monomers (b) is a mixture of R in formula (b1), (b2), or (b3). ｂ is preferably an ethylene group, a propylene group, or a butylene group. When a polyalkylene glycol di(meth)acrylate represented by formula (b2) is used, it is not preferable to use it alone as the monomer (b), but it is preferable to use it in combination with the monomer (b1). In that case, it is also preferable to keep the content of the compound represented by formula (b2) to less than 30% by weight of the monomer (b) used.

[0080] Specific examples of the monomer (b) can be exemplified by, for example, the following, but are not limited thereto. CH2=CHCOO-CH2CH2O-H CH2=CHCOO-CH2CH2CH2O-H CH2=CHCOO-CH2CH(CH3)O-H CH2=CHCOO-CH(CH3)CH2O-H CH2=CHCOO-CH2CH2CH2CH2O-H CH2=CHCOO-CH2CH2CH(CH3)O-H CH2=CHCOO-CH2CH(CH3)CH2O-H CH2=CHCOO-CH(CH3)CH2CH2O-H CH2=CHCOO-CH2CH(CH2CH3)O-H CH2=CHCOO-CH2C(CH3)2O-H CH2=CHCOO-CH(CH2CH3)CH2O-H CH2=CHCOO-C(CH3)2CH2O-H CH2=CHCOO-CH(CH3)CH(CH3)O-H CH2=CHCOO-C(CH3)(CH2CH3)O-H CH2=CHCOO-(CH2CH2O)2-H CH2=CHCOO-(CH2CH2O)4-H CH2=CHCOO-(CH2CH2O)5-H CH2=CHCOO-(CH2CH2O)6-H CH2=CHCOO-(CH2CH2O)5-CH3 CH2=CHCOO-(CH2CH2O)9-CH3 CH2=CHCOO-(CH2CH2O) 23 -CH3 CH2=CHCOO-(CH2CH2O) 90 -CH3

[0081] CH2=CHCOO-(CH2CH(CH3)O)9-H CH2=CHCOO-(CH2CH(CH3)O)9-CH3 CH2=CHCOO-(CH2CH(CH3)O) 12 -CH3 CH2=CHCOO-(CH2CH2O)5-(CH2CH(CH3)O)2-H CH2=CHCOO-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3 CH2=CHCOO-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9 CH2=CHCOO-(CH2CH2O) 23 -OOC(CH3)C=CH2 CH2=CHCOO-(CH2CH2O) 20 -(CH2CH(CH3)O)5-CH2-CH=CH2

[0082] CH2=CHCOO-(CH2CH2O)9-H CH2=C(CH3)COO-CH2CH2O-H CH2=C(CH3)COO-CH2CH2CH2O-H CH2=C(CH3)COO-CH2CH(CH3)O-H CH2=C(CH3)COO-CH(CH3)CH2O-H CH2=C(CH3)COO-CH2CH2CH2CH2O-H CH2=C(CH3)COO-CH2CH2CH(CH3)O-H CH2=C(CH3)COO-CH2CH(CH3)CH2O-H CH2=C(CH3)COO-CH(CH3)CH2CH2O-H CH2=C(CH3)COO-CH2CH(CH2CH3)O-H CH2=C(CH3)COO-CH2C(CH3)2O-H CH2=C(CH3)COO-CH(CH2CH3)CH2O-H CH2=C(CH3)COO-C(CH3)2CH2O-H CH2=C(CH3)COO-CH(CH3)CH(CH3)O-H CH2=C(CH3)COO-C(CH3)(CH2CH3)O-H CH2=C(CH3)COO-(CH2CH2O)2-H CH2=C(CH3)COO-(CH2CH2O)4-H CH2=C(CH3)COO-(CH2CH2O)5-H CH2=C(CH3)COO-(CH2CH2O)6-H CH2=C(CH3)COO-(CH2CH2O)9-H CH2=C(CH3)COO-(CH2CH2O)5-CH3 CH2=C(CH3)COO-(CH2CH2O)9-CH3 CH2=C(CH3)COO-(CH2CH2O) 23 -CH3 CH2=C(CH3)COO-(CH2CH2O) 90 -CH3 CH2=C(CH3)COO-(CH2CH(CH3)O)9-H

[0083] CH2=C(CH3)COO-(CH2CH(CH3)O)9-CH3 CH2=C(CH3)COO-(CH2CH(CH3)O) 12-CH3 CH2=C(CH3)COO-(CH2CH2O)5-(CH2CH(CH3)O)2-H CH2=C(CH3)COO-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3 CH2=C(CH3)COO-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9 CH2=C(CH3)COO-(CH2CH2O) 23 -OOC(CH3)C=CH2 CH2=C(CH3)COO-(CH2CH2O) 20 -(CH2CH(CH3)O)5-CH2-CH=CH2

[0084] CH2=CH-C(=O)-NH-CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH(CH3)OH CH2=CH-C(=O)-NH-CH(CH3)CH2O-H CH2=CH-C(=O)-NH-CH2CH2CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH2CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH(CH3)CH2O-H CH2=CH-C(=O)-NH-CH2C(CH3)2O-H CH2=CH-C(=O)-NH-CH(CH2CH3)CH2O-H CH2=CH-C(=O)-NH-C(CH3)2CH2O-H CH2=CH-C(=O)-NH-CH(CH3)CH(CH3)OH CH2=CH-C(=O)-NH-C(CH3)(CH2CH3)OH CH2=CH-C(=O)-NH-(CH2CH2O)2-H CH2=CH-C(=O)-NH-(CH2CH2O)4-H CH2=CH-C(=O)-NH-(CH2CH2O)5-H CH2=CH-C(=O)-NH-(CH2CH2O)6-H CH2=CH-C(=O)-NH-(CH2CH2O)9-H CH2=CH-C(=O)-NH-(CH2CH2O)5-CH3 CH2=CH-C(=O)-NH-(CH2CH2O)9-CH3 CH2=CH-C(=O)-NH-(CH2CH2O) 23-CH3 CH2=CH-C(=O)-NH-(CH2CH2O) 90 -CH3

[0085] CH2=CH-C(=O)-NH-(CH2CH(CH3)O)9-H CH2=CH-C(=O)-NH-(CH2CH(CH3)O)9-CH3 CH2=CH-C(=O)-NH-(CH2CH(CH3)O) 12 -CH3 CH2=CH-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)2-H CH2=CH-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3 CH2=CH-C(=O)-NH-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9

[0086] CH2=C(CH3)-C(=O)-NH-CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH(CH3)OH CH2=C(CH3)-C(=O)-NH-CH(CH3)CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH2CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH(CH2CH3)OH CH2=C(CH3)-C(=O)-NH-CH2C(CH3)2O-H CH2=C(CH3)-C(=O)-NH-CH(CH2CH3)CH2O-H CH2=C(CH3)-C(=O)-NH-C(CH3)2CH2O-H CH2=C(CH3)-C(=O)-NH-CH(CH3)CH(CH3)OH CH2=C(CH3)-C(=O)-NH-C(CH3)(CH2CH3)OH CH2=C(CH3)-C(=O)-NH-(CH2CH2O)2-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)4-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)6-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)9-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O)9-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O) 23 -CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O) 90 -CH3

[0087] CH2=C(CH3)-C(=O)-NH-(CH2CH(CH3)O)9-H CH2=C(CH3)-C(=O)-NH-(CH2CH(CH3)O)9-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH(CH3)O) 12-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)2-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9

[0088] The monomer (b) may be X ２ is a hydrogen atom. The monomer (b) is particularly preferably hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or hydroxyethyl acrylamide.

[0089] (c) Ionic Group-Containing Monomer The hydrocarbon group-containing polymer may contain a repeating unit derived from an ionic group-containing monomer (c). The monomer (c) is preferably a monomer containing one ethylenically unsaturated double bond and an ionic group (particularly, an acrylic monomer). The ionic group is an anionic group and / or a cationic group, or a salt thereof.

[0090] The monomer (c) preferably has a (meth)acrylic group as the ethylenically unsaturated double bond, and may have, for example, a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond.

[0091] Examples of the monomer having an anionic group include a monomer having a carboxyl group, a sulfonic acid group, or a phosphoric acid group. Specific examples of the monomer having an anionic group include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, vinylsulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, (meth)acrylate phosphate, vinylbenzenesulfonic acid, acrylamido-tertiarybutylsulfonic acid, and salts thereof.

[0092] Examples of salts of anionic groups include alkali metal salts, alkaline earth metal salts, and ammonium salts, such as methylammonium salts, ethanolammonium salts, and triethanolammonium salts.

[0093] In the monomer having a cationic group, examples of the cationic group are amino groups, preferably tertiary amino groups and quaternary amino groups. In the tertiary amino group, two groups bonded to the nitrogen atom may be the same or different and may be an aliphatic group having 1 to 5 carbon atoms (particularly an alkyl group), an aromatic group having 6 to 20 carbon atoms (aryl group), or an aromatic aliphatic group having 7 to 25 carbon atoms (particularly an aralkyl group, for example a benzyl group (C ６ H ５ -CH ２ In the quaternary amino group, the three groups bonded to the nitrogen atom are the same or different and are an aliphatic group having 1 to 5 carbon atoms (particularly an alkyl group), an aromatic group having 6 to 20 carbon atoms (aryl group), or an aromatic aliphatic group having 7 to 25 carbon atoms (particularly an aralkyl group, for example a benzyl group (C ６ H ５ -CH ２ In the tertiary amino group and the quaternary amino group, the remaining group bonded to the nitrogen atom may have an ethylenically unsaturated double bond. The cationic group may be in the form of a salt.

[0094] The cationic group in the form of a salt is a salt with an acid (organic acid or inorganic acid). Organic acids, such as carboxylic acids having 1 to 20 carbon atoms (particularly monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and stearic acid), are preferred. Dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate and salts thereof are preferred.

[0095] Specific examples of the monomer having a cationic group are as follows: CH2=CHCOO-CH2CH2-N(CH3)2 and its salts (e.g., acetate) CH2=CHCOO-CH2CH2-N(CH2CH3)2 and its salts (e.g., acetate) CH2=C(CH3)COO-CH2CH2-N(CH3)2 and its salts (e.g., acetate) CH2=C(CH3)COO-CH2CH2-N(CH2CH3)2 and its salts (e.g., acetate) CH2=CHC(O)N(H)-CH2CH2CH2-N(CH3)2 and its salts (e.g., acetate) CH2=CHCOO-CH2CH2-N(-CH3)(-CH2-C6H5) and its salts (e.g., acetate) CH2=C(CH3)COO-CH2CH2-N(-CH2CH3)(-CH2-C6H5) and its salts (e.g., acetate) CH2=CHCOO-CH2CH2-N + (CH3)3Cl - CH2=CHCOO-CH2CH2-N + (-CH3)2(-CH2-C6H5)Cl - CH2=C(CH3)COO-CH2CH2-N + (CH3)3Cl - CH2=CHCOO-CH2CH(OH)CH2-N + (CH3)3Cl - CH2=C(CH3)COO-CH2CH(OH)CH2-N + (CH3)3Cl - CH2=C(CH3)COO-CH2CH(OH)CH2-N + (-CH2CH3)2(-CH2-C6H5)Cl - CH2=C(CH3)COO-CH2CH2-N + (CH3)3Br - CH2=C(CH3)COO-CH2CH2-N + (CH3)3I - CH2=C(CH3)COO-CH2CH2-N + (CH3)3O - SO3CH3 CH2=C(CH3)COO-CH2CH2-N + (CH3)(-CH2-C6H5)2Br -

[0096] The ionic group-containing monomer (c) is preferably methacrylic acid, acrylic acid, or dimethylaminoethyl methacrylate, and more preferably methacrylic acid or dimethylaminoethyl methacrylate.

[0097] (d) Halogenated Olefin Monomer The hydrocarbon group-containing polymer may have a repeating unit derived from a halogenated olefin monomer (d). The halogenated olefin monomer (d) may not contain fluorine atoms. The halogenated olefin monomer (d) is preferably an olefin having 2 to 20 carbon atoms and substituted with 1 to 10 chlorine atoms, bromine atoms, or iodine atoms. The halogenated olefin monomer (d) is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly an olefin having 2 to 5 carbon atoms and having 1 to 5 chlorine atoms. Preferred examples of the halogenated olefin monomer (d) include vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide, and vinylidene halides such as vinylidene chloride, vinylidene bromide, and vinylidene iodide. Vinyl chloride or vinylidene chloride is preferred because it enhances water repellency (particularly the durability of water repellency). The presence of repeating units derived from the halogenated olefin monomer (d) improves the washing durability of the hydrocarbon group-containing polymer.

[0098] (e) Crosslinkable Monomer The hydrocarbon group-containing polymer may contain a repeating unit derived from a crosslinkable monomer (e). The crosslinkable monomer (e) has a reactive group and / or an ethylenically unsaturated double bond (preferably, a (meth)acrylate group). The crosslinkable monomer (e) may be a monomer that does not contain a fluorine atom. The crosslinkable monomer (e) may be a compound having at least two ethylenically unsaturated double bonds (preferably, a (meth)acrylate group), or a compound having at least one ethylenically unsaturated double bond and at least one reactive group. Examples of the reactive group include a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group, and a carboxyl group.

[0099] Examples of the crosslinkable monomer may be a vinyl monomer having a reactive group, a mono(meth)acrylate, a di(meth)acrylate or a di(meth)acrylamide having a reactive group.

[0100] Examples of crosslinkable monomers include, but are not limited to, diacetone (meth)acrylamide, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, butadiene, isoprene, chloroprene, vinyl monochloroacetate, vinyl methacrylate, glycidyl (meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate.

[0101] (f) Cyclic hydrocarbon group-containing monomer The hydrocarbon group-containing polymer may have a repeating unit derived from a cyclic hydrocarbon group-containing monomer (f). The cyclic hydrocarbon group-containing monomer (f) is a monomer having a cyclic hydrocarbon group, and may be a monomer having one ethylenically unsaturated double bond and a cyclic hydrocarbon group. The hydrocarbon group-containing polymer may be a styrene polymer having a repeating unit derived from styrene or a styrene derivative.

[0102] The cyclic hydrocarbon group-containing monomer (f) preferably has a (meth)acrylic group as the ethylenically unsaturated double bond, and may have, for example, a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond.

[0103] The cyclic hydrocarbon group may be alicyclic or aromatic. The cyclic hydrocarbon group may be saturated or unsaturated. The cyclic hydrocarbon group may be a monocyclic group, a polycyclic group, or a bridged ring group, with a bridged ring group being preferred. The cyclic hydrocarbon group may have a chain group (e.g., a halogen atom, a linear or branched chain hydrocarbon group (particularly a linear or branched chain hydrocarbon group having 1 to 20 carbon atoms)).

[0104] The cyclic hydrocarbon group may have 4 or more, 6 or more, or 8 or more carbon atoms, and may have 30 or less, 26 or less, 22 or less, 18 or less, or 14 or less carbon atoms.

[0105] Specific examples of the cyclic hydrocarbon group include a cyclohexyl group, a t-butylcyclohexyl group, an adamantyl group, a 2-methyl-2-adamantyl group, a 2-ethyl-2-adamantyl group, a bornyl group, an isobornyl group, a norbornyl group, a dicyclopentanyl group, a dicyclopentenyl group, a benzyl group, a phenyl group, a naphthyl group, a 2-t-butylphenyl group, residues obtained by removing one or more hydrogen atoms from these groups (for example, a cyclohexylene group, an adamantylene group, a phenylene group, a naphthylene group, etc.), and groups which are substitution products thereof.

[0106] Specific examples of the cyclic hydrocarbon group-containing monomer (f) include cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, and compounds in which these acrylates are substituted with acrylamide, etc. These may be used alone or in combination of two or more.

[0107] An example of the cyclic hydrocarbon group-containing monomer (f) is a styrene compound. The styrene compound may be modified with a chain group (for example, a halogen atom, or a linear or branched hydrocarbon group (particularly a linear or branched hydrocarbon group having 1 to 20 carbon atoms). Specific examples thereof include styrene, 4-t-butylstyrene, 3,5-di-t-butylstyrene, 2,4,6-tri-t-butylstyrene, 4-methylstyrene, 3,5-dimethylstyrene, and 2,4,6-trimethylstyrene. The styrene compound may be an α-methylstyrene compound or an α-chlorostyrene compound in which the α-position is a chlorine atom, or may be a styrene compound in which the α-position is a hydrogen atom.

[0108] (g) Other Monomers The other monomers are not limited to these examples and include acrylonitrile, short-chain alkyl (meth)acrylate, vinyl acetate, vinyl alkyl ether, polysiloxane group-containing monomers, etc. The other monomers (g) may be used alone or in combination of two or more.

[0109] [Polymer composition] The hydrocarbon group-containing polymer in the present disclosure is mainly composed of repeating units derived from a hydrocarbon group-containing monomer (a1), and the amount of the hydrophilic group-containing monomer (b) or the ionic group-containing monomer (c) is preferably small. The hydrophilic group-containing monomer (b) and the ionic group-containing monomer (c) are involved in dispersibility and adhesion to a substrate (pulp substrate) and contribute to improving oil resistance. However, despite the reduction in the amount of these monomers, by increasing the constituent ratio of the hydrocarbon group-containing monomer to more than 90%, an unexpected effect was found that oil resistance can be maintained even after long-term stirring.

[0110] The combination of monomers (a) to (g) constituting the repeating units of the hydrocarbon group-containing polymer is not particularly limited, but examples are as follows (brackets are omitted): a a+b a+b+c a+c a+d a+b+c+d a+b+c+d+e a+b+c+d+e+f Another monomer (h) may be used in combination with the above combination. For pulp products, it is preferable to use monomer (a), monomer (b), and monomer (c) in combination. In the above combination, monomer (a) may be monomer (a1), but monomer (a2) may also be used in combination.

[0111] The amount of the monomer (a), relative to the hydrocarbon group-containing polymer, may be more than 90% by weight, 92% by weight or more, 94% by weight or more, 96% by weight or more, 98% by weight or more, 99% by weight or more, 99.5% by weight or more, or 100% by weight, and is preferably more than 97% by weight and 100% by weight or less, 99% by weight or less, 97% by weight or less, 95% by weight or less, or 93% by weight or less, and in one aspect, more than 90% by weight and 100% by weight or less.

[0112] The amount of the monomer (a1) may be more than 90% by weight, 92% by weight or more, 94% by weight or more, 96% by weight or more, 98% by weight or more, 99% by weight or more, 99.5% by weight or more, or 100% by weight, based on the hydrocarbon group-containing polymer, and is, for example, 93% by weight or more, preferably more than 97% by weight, and is 100% by weight or less, 99% by weight or less, 97% by weight or less, 95% by weight or less, or 93% by weight or less, and in one embodiment, more than 90% by weight and 100% by weight or less. The amount of the monomer (a1) may be 100% by weight based on the hydrocarbon group-containing polymer.

[0113] The amount of monomer (a2) may be 0% by weight or more, 0.1% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, or 8% by weight or more of monomer (a), and may be 10% by weight or less, 8% by weight or less, 6% by weight or less, 4% by weight or less, 2% by weight or less, 1% by weight or less, or 0% by weight, and in one aspect, is 0% by weight or more and less than 7% by weight, or 0% by weight or more and less than 3% by weight.

[0114] The amount of repeating units derived from the monomer (b) may be 0% by weight or more, 0.1% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, or 8% by weight or more, and may be 10% by weight or less, 8% by weight or less, 6% by weight or less, 4% by weight or less, 2% by weight or less, 1% by weight or less, or 0% by weight, and in one embodiment, is 0% by weight or more and less than 7% by weight, or 0% by weight or more and less than 3% by weight, based on the hydrocarbon group-containing polymer.

[0115] The amount of repeating units derived from monomer (c) may be 0% by weight or more, 0.1% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, or 8% by weight or more, and may be 10% by weight or less, 8% by weight or less, 6% by weight or less, 4% by weight or less, 2% by weight or less, 1% by weight or less, or 0% by weight, and in one embodiment, is 0% by weight or more and less than 7% by weight, or 0% by weight or more and less than 3% by weight, based on the hydrocarbon group-containing polymer.

[0116] The amount of repeating units derived from the monomer (d) may be 0% by weight or more, 0.1% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, or 8% by weight or more, and may be 10% by weight or less, 8% by weight or less, 6% by weight or less, 4% by weight or less, 2% by weight or less, 1% by weight or less, or 0% by weight, and in one embodiment, is 0% by weight or more and less than 7% by weight, or 0% by weight or more and less than 3% by weight, based on the hydrocarbon group-containing polymer.

[0117] The amount of repeating units derived from monomer (e) may be 0% by weight or more, 0.1% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, or 8% by weight or more, and may be 10% by weight or less, 8% by weight or less, 6% by weight or less, 4% by weight or less, 2% by weight or less, 1% by weight or less, or 0% by weight, and in one embodiment, is 0% by weight or more and less than 7% by weight, or 0% by weight or more and less than 3% by weight, based on the hydrocarbon group-containing polymer.

[0118] The amount of repeating units derived from the monomer (f) may be 0% by weight or more, 0.1% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, or 8% by weight or more, and may be 10% by weight or less, 8% by weight or less, 6% by weight or less, 4% by weight or less, 2% by weight or less, 1% by weight or less, or 0% by weight, and in one embodiment, is 0% by weight or more and less than 7% by weight, or 0% by weight or more and less than 3% by weight, based on the hydrocarbon group-containing polymer.

[0119] The amount of repeating units derived from the monomer (g) may be 0% by weight or more, 0.1% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, or 8% by weight or more, and may be 10% by weight or less, 8% by weight or less, 6% by weight or less, 4% by weight or less, 2% by weight or less, 1% by weight or less, or 0% by weight, and in one embodiment, is 0% by weight or more and less than 7% by weight, or 0% by weight or more and less than 3% by weight, based on the hydrocarbon group-containing polymer.

[0120] [Polymerization Method] The hydrocarbon group-containing polymer can be produced by a known polymerization method, and the polymerization reaction conditions can be selected arbitrarily. Examples of such polymerization methods include solution polymerization, suspension polymerization, emulsion polymerization, and condensation polymerization.

[0121] In solution polymerization, a method is employed in which monomers are dissolved in an organic solvent in the presence of a polymerization initiator, and after purging with nitrogen, the mixture is heated and stirred at a temperature in the range of 30 to 120°C for 1 to 10 hours. Examples of polymerization initiators include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight, per 100 parts by weight of the monomers.

[0122] The organic solvent is inert to the monomers and dissolves them, and may be, for example, an ester (e.g., an ester having 2 to 40 carbon atoms, specifically, ethyl acetate, butyl acetate), a ketone (e.g., a ketone having 2 to 40 carbon atoms, specifically, methyl ethyl ketone, diisobutyl ketone, methyl isobutyl ketone), or an alcohol (e.g., an alcohol having 1 to 40 carbon atoms, specifically, ethanol, butanol, isopropyl alcohol). Specific examples of the organic solvent include acetone, chloroform, HCHC225, isopropyl alcohol, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, and trichlorotrifluoroethane. The organic solvent is used in an amount of 10 to 3,000 parts by weight, for example, 50 to 2,000 parts by weight, per 100 parts by weight of the total of the monomers.

[0123] Emulsion polymerization involves emulsifying monomers in water in the presence of a polymerization initiator and an emulsifier, purging with nitrogen, and then polymerizing the mixture at a temperature ranging from 50 to 80°C for 1 to 20 hours with stirring. Examples of polymerization initiators that can be used include water-soluble initiators such as benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, sodium peroxide, potassium persulfate, and ammonium persulfate, as well as oil-soluble initiators such as azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount ranging from 0.01 to 10 parts by weight per 100 parts by weight of the monomer.

[0124] To obtain a polymer aqueous dispersion with excellent shelf stability, it is desirable to polymerize the monomer by microparticulating it in water using an emulsifying device capable of applying powerful crushing energy, such as a high-pressure homogenizer or ultrasonic homogenizer. Furthermore, various anionic, cationic, or nonionic emulsifiers can be used as emulsifiers, and are used in a range of 0.5 to 20 parts by weight per 100 parts by weight of monomer. It is preferable to use anionic and / or nonionic and / or cationic emulsifiers. If the monomers are not completely compatible, it is preferable to add a compatibilizer, such as a water-soluble organic solvent or a low-molecular-weight monomer, that will fully compatibilize these monomers. Addition of a compatibilizer can improve emulsification and copolymerization properties.

[0125] The water-soluble organic solvent may be any of the organic solvents described above. Examples include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, and ethanol. These may be used in an amount of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, per 100 parts by weight of water. Examples of low-molecular-weight monomers include methyl methacrylate, glycidyl methacrylate, and 2,2,2-trifluoroethyl methacrylate. These may be used in an amount of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, per 100 parts by weight of the total amount of monomers.

[0126] A chain transfer agent may be used in the polymerization. The molecular weight of the polymer can be changed depending on the amount of chain transfer agent used. Examples of chain transfer agents include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (particularly alkyl mercaptans (e.g., having 1 to 40 carbon atoms)), and inorganic salts such as sodium hypophosphite and sodium hydrogen sulfite. The amount of chain transfer agent used may be in the range of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, per 100 parts by weight of the total amount of monomers.

[0127] [Amount of Polymer] The amount of the hydrocarbon group-containing polymer in the repellent may be 0.01% by weight or more, 0.03% 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, or 30% by weight or more, or may be 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 hydrocarbon group-containing polymer itself may be used as the repellent.

[0128] [Lignin Compound] The repellent of the present disclosure contains a lignin compound. By including the lignin compound, the effects of the present disclosure can be effectively achieved. For example, by including the lignin compound, the stability of the repellent when it is made into an aqueous dispersion can be improved.

[0129] In the present disclosure, the lignin compound is a compound selected from lignin and modified lignin. The modified lignin is a compound whose main component is a structure derived from lignin, in which a portion of the lignin has been chemically modified and / or decomposed into smaller molecules, and may be a lignin derivative, a decomposition product of lignin, a derivative of a decomposition product of lignin, or the like. Specific examples of the lignin compound include lignin, lignosulfonic acid, kraft lignin, soda lignin, soda-anthraquinone lignin, organosolv lignin, explosive lignin, and sulfuric acid lignin. Of these, lignosulfonic acid and kraft lignin are preferred.

[0130] The lignin compound has phenolic hydroxyl groups, and the amount of phenolic hydroxyl groups may be 1.5% or more, preferably 1.6% or more, more preferably 1.7% or more, and may be 20% or less, 15% or less, 10% or less, or 6.0% or less, preferably 5.5% or less, more preferably 5.0% or less, and in one aspect, 1.5 to 6.0%, 1.6 to 5.5%, or 1.7 to 5.0%. Furthermore, when the lignin compound is kraft lignin, the amount of phenolic hydroxyl groups is more preferably 2.0% or more, and particularly preferably more than 2.5%.

[0131] The amount of phenolic hydroxyl groups can be measured by measuring the differential extinction coefficient around 300 nm using a spectrophotometer. For example, an ionization differential spectrum is obtained by subtracting the absorption spectrum of a neutral solution containing the same concentration of lignin from the absorption spectrum of an alkaline solution containing the lignin sample (lignin compound). The amount of phenolic hydroxyl groups (%) is calculated using the following formula: Amount of phenolic hydroxyl groups (%) = 17 × Δαmax / 4100 × 100. Δαmax [L / (g cm)] represents the differential extinction coefficient. For details, see "Lignin Chemistry: Fundamentals and Applications," edited by Junzo Nakano, Uni Publishing, May 25, 1990, p. 541.

[0132] The weight average molecular weight of the lignin compound may be 500 or more, 1,000 or more, 2,000 or more, 3,000 or more, or 5,000 or more, preferably 1,000 or more, and may be 500,000 or less, 300,000 or less, 100,000 or less, 50,000 or less, or 30,000 or less, preferably 50,000 or less. The weight average molecular weight may be a polyethylene glycol-equivalent molecular weight measured by GPC.

[0133] The lignin compound may have a functional group (particularly an ionic group) other than a phenolic hydroxyl group. Examples of such a functional group include a hydroxyl group, a carboxyl group, a polyalkylene oxide chain, a sulfonic acid group, a nitroxyl group, a carbonyl group, a phosphate group, an amino group, an epoxy group, a methylol group, a cyanate group, an isocyanate group, a vinyl group, and a maleimide group. An ionic group is particularly preferred, and an anionic group is preferable. This can further improve dispersibility. Examples of such functional groups include a carboxyl group, a sulfonic acid group, and a phosphate group. Among these, a sulfonic acid group is more preferred.

[0134] Lignin compounds have phenolic hydroxyl groups and may also have ionic groups, and therefore function as ionic dispersants (ionic surfactants), particularly anionic dispersants (anionic surfactants).

[0135] The lignin compound preferably has a sulfur-containing functional group such as a sulfo group or a thiol group, and the sulfur content may be 0.1% by mass or more, 0.3% by mass or more, 0.5% by mass or more, or 6% by mass or less, 5% by mass or less, 4% by mass or less, or 3% by mass or less.

[0136] The functional groups in the lignin compound can be quantitatively or qualitatively measured by instrumental analysis such as NMR, IR, and elemental analysis.

[0137] The lignin compound may contain structural units derived from other compounds, such as (alkyl)phenols (e.g., phenol and cresol), aromatic hydrocarbon compounds (e.g., benzene and naphthalene), etc., within the scope of the present disclosure.

[0138] It is difficult to uniformly specify the chemical structure of lignin compounds using a general formula or the like because the skeleton that constitutes lignin compounds has a very complex molecular structure.

[0139] The lignin compound may be in the form of a salt, for example, an alkali metal salt such as a sodium salt or a potassium salt, an alkaline earth metal salt such as a calcium salt, an ammonium salt, or a salt of an organic amine.

[0140] [Lignosulfonic Acid] The lignin compound is preferably lignosulfonic acid, which is a lignin compound modified with a sulfo group, and may be, for example, a compound having a skeleton in which a carbon atom at the α-position of the side chain of the hydroxyphenylpropane structure of lignin is cleaved to introduce a sulfo group.

[0141] The lignosulfonic acid may be a lignosulfonate salt, and examples of the salt include alkali metal salts such as sodium salts or potassium salts, alkaline earth metal salts such as calcium salts, ammonium salts, and salts of organic amines, such as sodium lignosulfonate.

[0142] As the lignin sulfonic acid, commercially available products may be used, such as Vanilex HW (manufactured by Nippon Paper Industries Co., Ltd.), Sunex M (manufactured by Nippon Paper Industries Co., Ltd.), Pearlex NP (manufactured by Nippon Paper Industries Co., Ltd.), Sunflow RH (manufactured by Nippon Paper Industries Co., Ltd.), POLYFON, and REAX (all manufactured by Ingevity).

[0143] [Amount of Lignin Compound] The amount of the lignin compound may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the hydrocarbon group-containing polymer, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less.

[0144] [Dispersant] The repellent of the present disclosure may contain a dispersant. The dispersant may be at least one selected from an organic dispersant and an inorganic dispersant. The dispersant may be at least one selected from an anionic dispersant, a nonionic dispersant, a cationic dispersant, an amphoteric dispersant, and an inorganic dispersant. In particular, the repellent of the present disclosure may contain a nonionic dispersant.

[0145] As the dispersant, an organic dispersant and an inorganic dispersant may be used individually, or a combination of an organic dispersant and an inorganic dispersant may be used.

[0146] An organic dispersant may be used as the dispersant. The organic dispersant can be classified into a nonionic dispersant, an anionic dispersant, a cationic dispersant, and an amphoteric dispersant, and the organic dispersant may refer to a surfactant.

[0147] The dispersant may not have a fluorine atom.

[0148] [Nonionic Dispersant] The dispersant may contain a nonionic dispersant, which may be a nonionic surfactant.

[0149] The nonionic dispersant may be a low molecular weight type (e.g., a molecular weight of 2000 or less, particularly 10,000 or less) or a high molecular weight type (e.g., a molecular weight of 2000 or more). The molecular weight of the nonionic dispersant may be 100 or more, 500 or more, 1,000 or more, 2,000 or more, 4,000 or more, or 6,000 or more, or may be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0150] Examples of nonionic dispersants include ethers, esters, ester ethers, alkanolamides, polyols and amine oxides.

[0151] An example of an ether is a compound having an oxyalkylene group (preferably a polyoxyethylene group).

[0152] An example of the ester is an ester of an alcohol and a fatty acid. An example of the alcohol is a mono- to trio-hydric (particularly di- to deca-hydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 10 to 30 carbon atoms). An example of the fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0153] An example of an ester ether is a compound in which an alkylene oxide (particularly ethylene oxide) is added to an ester of an alcohol and a fatty acid. An example of an alcohol is a mono- to trio-hydric (particularly di- to deca-hydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms). An example of a fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0154] Examples of alkanolamides are those formed from fatty acids and alkanolamines. The alkanolamides may be monoalkanolamides or dialkanolamines. Examples of fatty acids include saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. The alkanolamines may be alkanols having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, and having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0155] The polyol may be a di- to penta-hydric alcohol having 10 to 30 carbon atoms. The amine oxide may be an oxide (for example, having 5 to 50 carbon atoms) of an amine (secondary amine or preferably tertiary amine).

[0156] The nonionic dispersant is preferably a nonionic dispersant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms in the alkylene group in the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic dispersant is generally preferably 2 to 100.

[0157] The nonionic dispersant is selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyols and amine oxides, and is preferably a nonionic dispersant having an oxyalkylene group.

[0158] The nonionic dispersant may be an alkylene oxide adduct of a linear and / or branched aliphatic (saturated and / or unsaturated) group, a polyalkylene glycol ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a sorbitan ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a glycerin ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyglycerin ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a sucrose ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of acetylene glycol, or the like. Among these, those in which the alkylene oxide adduct moiety and the polyalkylene glycol moiety have a structure of polyoxyethylene (POE), polyoxypropylene (POP), or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred. Furthermore, the nonionic dispersant does not have to contain an aromatic group.

[0159] The nonionic dispersant has the formula: １ O-(CH ２ CH ２ O) ｐ - (R ２ O) ｑ -R ３ [In the formula, R １ is an alkyl group having 1 to 22 carbon atoms, or an alkenyl group or acyl group having 2 to 22 carbon atoms, ２ are independently the same or different and are alkylene groups having 3 or more carbon atoms (e.g., 3 to 10), ３ is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms, p is a number of 2 or more, and q is a number of 0 or 1 or more.

[0160] R １ R preferably has 8 to 20 carbon atoms, particularly 10 to 18 carbon atoms. １Preferred specific examples of R include an octyl group, a nonyl group, a trimethylnonyl group, a lauryl group, a tridecyl group, an oleyl group, and a stearyl group. ２ Examples of the nonionic dispersant are a propylene group and a butylene group. In the nonionic dispersant, p may be a number of 3 or more (for example, 5 to 200). q may be a number of 2 or more (for example, 5 to 200). That is, -(R ２ O) ｑ - may form a polyoxyalkylene chain. The nonionic dispersant may be a polyoxyethylene alkylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) at the center. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, and a styrene chain, with the oxypropylene chain being preferred.

[0161] Specific examples of nonionic dispersants include ethylene oxide and hexylphenol, isooctatylphenol, hexadecanol, oleic acid, alkanes (C １２ -C １６ ) thiol, sorbitan mono fatty acid (C ７ -C １９ ) or alkyl (C １２ -C １８ ) condensation products with amines, etc., sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, lecithin derivatives, etc. Examples of nonionic dispersants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene polyoxybutylene alkyl ethers, polyoxyethylene polyoxypropylene glycol, polyethyleneimine ethoxylate, etc.

[0162] The proportion of polyoxyethylene blocks can be 5 to 80% by weight, for example 30 to 75% by weight, and particularly 40 to 70% by weight, based on the molecular weight of the nonionic dispersant (copolymer). The average molecular weight of the nonionic dispersant is generally 300 to 5,000, for example 500 to 3,000. The nonionic dispersant may be a single type or a mixture of two or more types. The nonionic dispersant may be a mixture of a compound having an HLB (hydrophilic-hydrophobic balance) of less than 15 (particularly 5 or less) and a compound having an HLB of 15 or more. Specifically, it is preferable to select from polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene, and polyoxypropylenes having an HLB value of 1 to 18, and sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene glycerin fatty acid esters, and polyoxyethylene sorbitan fatty acid esters having an HLB value of less than 7.

[0163] [Cationic Dispersant] The dispersant may contain a cationic dispersant. The cationic dispersant may be a cationic surfactant. The cationic dispersant may be a compound having no amide group.

[0164] The cationic dispersant may be a low molecular weight type (e.g., a molecular weight of 2000 or less, particularly 10,000 or less) or a high molecular weight type (e.g., a molecular weight of 2000 or more). The molecular weight of the cationic dispersant may be 100 or more, 500 or more, 1,000 or more, 2,000 or more, 4,000 or more, or 6,000 or more, and may be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0165] The cationic dispersant may be aliphatic or aromatic, and examples thereof include ammonium salts (e.g., quaternary ammonium salts). The cationic dispersant may be an oxyethylene adduct ammonium salt. Specific examples include amine salt-type dispersants such as alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazolines; quaternary ammonium salt-type dispersants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzalkonium chloride, and benzethonium chloride; and polymer-type cationic dispersants such as Polyquaternium-1 to 47. Examples of cationic dispersants include alkylamine salts and quaternary ammonium salts.

[0166] The low molecular weight cationic dispersant is R ２１ -N ＋ (-R ２２ ) (-R ２３ ) (-R ２４ ) X － [In the formula, R ２１ , R ２２ , R ２３ and R ２４ is hydrogen or a hydrocarbon group having 1 to 40 carbon atoms, and X is an anionic group. ２１ , R ２２ , R ２３ and -R ２４ Specific examples of X include alkyl groups (e.g., methyl, butyl, stearyl, and palmityl groups) and aromatic groups (e.g., benzyl and phenyl groups). Specific examples of X include halogens (e.g., chlorine) and acids (e.g., hydrochloric acid and acetic acid). Examples of cationic dispersants include monoalkyltrimethylammonium salts (alkyl having 4 to 40 carbon atoms) and benzalkonium chloride.

[0167] Specifically, the low molecular weight cationic dispersant is represented by the formula: １ ｐ -N ＋ R ２ ｑ X － [In the formula, R １ is C12 or more (e.g. C１２ ~C ５０ ) is a linear and / or branched aliphatic (saturated and / or unsaturated) group of the formula R ２ is H or a C1-4 alkyl group, a benzyl group, a polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (particularly 2, particularly 3) to 50) (CH ３ , C ２ H ５ is particularly preferred), and X is a halogen atom (e.g., chlorine), or C １ ~C ４ or a fatty acid salt of C １ ~C ４ where p is 1 or 2, q is 2 or 3, and p+q=4. １ may have 12 to 50 carbon atoms, for example, 12 to 30 carbon atoms.

[0168] Examples of low molecular weight cationic dispersants include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydropolyoxyethylene)ammonium chloride, benzyldodecyldi(hydropolyoxyethylene)ammonium chloride, N-[2-(diethylamino)ethyl]oleamide hydrochloride, and the like.

[0169] The polymeric cationic dispersant may be any of various polymers (e.g., polyquaternium-1 to -47) having a cationic group (e.g., ammonium group, quaternary ammonium group). Examples of the polymeric cationic dispersant include cationic natural products (particularly cationic sugars) such as cationic starch, cationic cellulose (e.g., O-(2-hydroxy-3-(trimethylammonio)propylhydroxyethylcellulose chloride), cationic guar gum, cationic xanthan gum, and chitosan; and polymers of cationic group-containing monomers such as aziridine, vinylimidazole, aminoalkyl methacrylate, N,N,N',N'-tetramethyl-2-butene-1,4-diamine, quaternized dimethylammonium ethyl methacrylate, diallyldimethylammonium chloride, dimethylaminopropylamine, and quaternized vinylimidazole.

[0170] [Anionic Dispersant] The dispersant may contain an anionic dispersant. The anionic dispersant may be an anionic surfactant. The dispersant may not contain an anionic dispersant.

[0171] The anionic dispersant may be a low molecular weight type (e.g., a molecular weight of 2000 or less, particularly 10,000 or less) or a high molecular weight type (e.g., a molecular weight of 2000 or more). The molecular weight of the anionic dispersant may be 100 or more, 500 or more, 1,000 or more, 2,000 or more, 4,000 or more, or 6,000 or more, and may be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 25,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 2,500 or less, 750 or less, or 250 or less.

[0172] Examples of anionic dispersants include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkanesulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfonic acid salts, N-acylamino acid type dispersants, phosphate mono- or diester type dispersants, and sulfosuccinate esters. An example of an anionic dispersant is a carboxylate (e.g., a fatty acid salt).

[0173] [Amphoteric Dispersant] The dispersant may contain an amphoteric dispersant, which may be an amphoteric surfactant.

[0174] The amphoteric dispersant may be a low molecular weight type (e.g., molecular weight of 2000 or less, particularly 10,000 or less) or a high molecular weight type (e.g., molecular weight of 2000 or more). The molecular weight of the amphoteric dispersant may be 100 or more, 500 or more, 1,000 or more, 2,000 or more, 4,000 or more, or 6,000 or more, and may be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 25,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 2,500 or less, 750 or less, or 250 or less.

[0175] Examples of amphoteric dispersants include alanines, imidazolinium betaines, amido betaines, and acetic acid betaine, and specific examples include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylamino acetic acid betaine, and fatty acid amidopropyl dimethylamino acetic acid betaine.

[0176] [Inorganic Dispersant] The dispersant may contain an inorganic dispersant.

[0177] The average primary particle size of the inorganic dispersant may be 5 nm or more, 30 nm or more, 100 nm or more, 1 μm or more, 10 μm or more, or 25 μm or more, and may be 100 μm or less, 50 μm or less, 10 μm or less, 1 μm or less, 500 nm or less, or 300 nm or less. The average primary particle size can be measured, for example, by observation with a microscope (scanning electron microscope or transmission electron microscope). The inorganic dispersant may be hydrophilic particles.

[0178] Examples of inorganic dispersants include polyvalent metal phosphates such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, and hydroxyapatite; carbonates such as calcium carbonate and magnesium carbonate; silicates such as calcium metasilicate; sulfates such as calcium sulfate and barium sulfate; and hydroxides such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide.

[0179] [Amount of Dispersant] The amount of dispersant may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the hydrocarbon group-containing polymer, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less.

[0180] [Liquid Medium] The repellent agent of the present disclosure may contain a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The repellent agent may be a dispersion or a solution. The repellent agent of the present disclosure is preferably a water dispersion.

[0181] Examples of organic solvents include esters (e.g., esters having 2 to 40 carbon atoms, specifically, ethyl acetate and butyl acetate), ketones (e.g., ketones having 2 to 40 carbon atoms, specifically, methyl ethyl ketone and diisobutyl ketone), alcohols (e.g., alcohols having 1 to 40 carbon atoms, specifically, isopropyl alcohol), aromatic solvents (e.g., toluene and xylene), and petroleum solvents (e.g., alkanes having 5 to 10 carbon atoms, specifically, naphtha and kerosene). The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent may contain a compound having at least one hydroxy group (e.g., alcohol, polyols such as glycol-based solvents, ethers of polyols (e.g., monoethers), etc.). These may be used alone or in combination.

[0182] [Amount of Liquid Medium] The amount of the liquid medium may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 1 part by weight of the hydrocarbon group-containing polymer.

[0183] The amount of water may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 1 part by weight of the hydrocarbon group-containing polymer.

[0184] The amount of the organic solvent may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 1 part by weight of the hydrocarbon group-containing polymer.

[0185] [Silicone] The oil-resistant agent according to the present disclosure may contain silicone (polyorganosiloxane). By containing silicone, it is possible to obtain good texture and durability in addition to good liquid repellency.

[0186] As the silicone, known silicones can be used, and examples of silicones include polydimethylsiloxane and modified silicones (amino-modified, epoxy-modified silicone, carboxy-modified silicone, methylhydrogen silicone, etc.). The silicone may be a silicone wax having wax-like properties. These may be used alone or in combination of two or more.

[0187] The weight average molecular weight of the silicone may be 1,000 or more, 10,000 or more, or 50,000 or more, and may be 2,500,000 or less, 1,000,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, or 50,000 or less.

[0188] [Amount of Silicone] The amount of silicone may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the hydrocarbon-containing polymer, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0189] [Wax] The oil-resistant agent according to the present disclosure may contain wax, which can impart good liquid repellency to the substrate.

[0190] Examples of waxes include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin wax (polyethylene wax, polypropylene wax, etc.), oxidized polyolefin wax, silicone wax, animal and vegetable wax, and mineral wax. Hydrocarbon wax, particularly paraffin wax, is preferred. Specific examples of compounds constituting the wax include normal alkanes (e.g., tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, and hexatriacontane), and normal alkenes (e.g., eicosene, docosene, tricosene, tetracosene, pentacosene, hexacosene, heptacosene, octacosene, nonacosene, triacontene, hentriacontene, dotriacontene, tritriacontene, tetratriacontene, pentatriacontene, and hexatriacontene (e.g., these 1-alkenes)). The number of carbon atoms in the compound constituting the wax is preferably 20 to 60, for example, 25 to 45. The molecular weight of the wax may be 200 to 2000, for example, 250 to 1500, or 300 to 1000. These may be used alone or in combination of two or more.

[0191] The melting point of the wax may be 50° C. or higher, 55° C. or higher, 60° C. or higher, 65° C. or higher, or 70° C. or higher, preferably 55° C. or higher, more preferably 60° C. or higher, and may be 200° C. or lower, 150° C. or lower, 130° C. or lower, 120° C. or lower, 110° C. or lower, 100° C. or lower, 80° C. or lower, or 50° C. or lower, preferably 120° C. or lower. The melting point of the wax is measured in accordance with JIS K 2235-1991.

[0192] [Amount of Wax] The amount of wax may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the hydrocarbon-containing polymer, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0193] [Organic Acid] The repellent of the present disclosure may contain an organic acid. Known organic acids can be used. Preferred organic acids include carboxylic acids, sulfonic acids, sulfinic acids, etc., with carboxylic acids being particularly preferred. Examples of the carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid, etc., with formic acid or acetic acid being particularly preferred. In the present disclosure, one type of organic acid may be used, or two or more types may be used in combination. For example, formic acid and acetic acid may be used in combination.

[0194] [Amount of Organic Acid] The amount of organic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the hydrocarbon group-containing polymer, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less. The amount of organic acid may be adjusted so that the pH of the repellent is 3 to 10, for example, 5 to 9, particularly 6 to 8. The repellent may be acidic (pH 7 or less, for example, 6 or less).

[0195] [Inorganic Acid] The repellent of the present disclosure may contain an inorganic acid. Known inorganic acids can be used. Examples of inorganic acids include hydrogen chloride, hydrogen bromide, hydrogen iodide, nitric acid, boric acid, sulfuric acid, and phosphoric acid. In the present disclosure, one type of inorganic acid may be used, or two or more types may be used in combination. Adding an inorganic acid can improve the stability of the aqueous dispersion.

[0196] [Amount of Inorganic Acid] The amount of inorganic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the hydrocarbon group-containing polymer, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less. The amount of inorganic acid may be adjusted so that the pH of the repellent is 3 to 10, for example, 5 to 9, particularly 6 to 8. The repellent may be acidic (pH 7 or less, for example, 6 or less).

[0197] [Hardening Agent] The repellent of the present disclosure may contain a hardening agent (an active hydrogen-reactive compound or an active hydrogen-containing compound). When the repellent is for paper (e.g., an oil-proofing agent for paper), it does not need to contain a hardening agent.

[0198] The curing agent (crosslinking agent) in the repellent agent can cure the agent well. The curing agent may be an active hydrogen-reactive compound or an active hydrogen-containing compound that reacts with active hydrogen or an active hydrogen-reactive group. Examples of active hydrogen-reactive compounds are isocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds, and hydrazide compounds. Examples of active hydrogen-containing compounds are hydroxyl group-containing compounds, amino group-containing compounds, carboxyl group-containing compounds, ketone group-containing compounds, hydrazide compounds, and melamine compounds.

[0199] The curing agent may contain an isocyanate compound. The isocyanate compound may be a polyisocyanate compound. The polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound functions as a crosslinking agent. Examples of polyisocyanate compounds include aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates. The isocyanate compound may be a blocked isocyanate compound (for example, a blocked polyisocyanate compound). The blocked isocyanate compound is a compound in which the isocyanate group of an isocyanate compound is masked with a blocking agent to inhibit reaction.

[0200] Examples of aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate, Aliphatic diisocyanates such as cyanatomethyl caproate, and aliphatic triisocyanates such as lysine ester triisocyanate, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, and 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane. These may be used alone or in combination of two or more.

[0201] Examples of alicyclic polyisocyanates include alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of alicyclic polyisocyanates include 1,3-cyclopentene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), and 1,3,5-triisocyanatocyclohexane. These may be used alone or in combination of two or more.

[0202] Examples of araliphatic polyisocyanates include araliphatic diisocyanates and araliphatic triisocyanates. Specific examples of araliphatic polyisocyanates include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethylxylylene diisocyanate) or a mixture thereof, and 1,3,5-triisocyanatomethylbenzene. These may be used alone or in combination of two or more.

[0203] Examples of aromatic polyisocyanates include aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate or a mixture thereof, 2,4- or 2,6-tolylene diisocyanate or a mixture thereof, triphenylmethane-4,4',4''-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate. These may be used alone or in combination of two or more.

[0204] Examples of the polyisocyanate derivatives include various derivatives of the above-mentioned polyisocyanate compounds, such as dimers, trimers, biurets, allophanates, carbodiimides, uretdiones, uretimines, isocyanurates, and iminooxadiazinediones. These may be used alone or in combination of two or more.

[0205] These polyisocyanates can be used alone or in combination of two or more. As the polyisocyanate compound, it is preferable to use a blocked polyisocyanate compound (blocked isocyanate), which is a compound in which the isocyanate group of a polyisocyanate compound is blocked with a blocking agent. It is preferable to use a blocked polyisocyanate compound because it is relatively stable in solution and can be used in the same solution as the repellent.

[0206] The blocking agent blocks free isocyanate groups. When the blocked polyisocyanate compound is heated to, for example, 100°C or higher, e.g., 130°C or higher, the isocyanate groups are regenerated and can easily react with hydroxyl groups. Examples of blocking agents include phenolic compounds, lactam compounds, aliphatic alcohol compounds, and oxime compounds. The polyisocyanate compounds can be used alone or in combination of two or more.

[0207] An epoxy compound is a compound having an epoxy group. Examples of epoxy compounds include epoxy compounds having a polyoxyalkylene group, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether. A chloromethyl group-containing compound is a compound having a chloromethyl group. An example of a chloromethyl group-containing compound is chloromethyl polystyrene. A carboxyl group-containing compound is a compound having a carboxyl group. Examples of a carboxyl group-containing compound are (poly)acrylic acid, (poly)methacrylic acid, etc.

[0208] Specific examples of ketone group-containing compounds include (poly)diacetone acrylamide and diacetone alcohol. Specific examples of hydrazide compounds include hydrazine, carbohydrazide, and adipic acid hydrazide. Specific examples of melamine compounds include melamine resins and methyl etherified melamine resins.

[0209] [Amount of Curing Agent] The amount of the curing agent may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the hydrocarbon group-containing polymer, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0210] [Other Components] The repellent may contain other components in addition to the above-mentioned components. Examples of other components include polysaccharides, flocculants, retention aids, coagulants, binder resins, anti-slip agents, sizing agents, paper strength agents, fillers, antistatic agents, preservatives, UV absorbers, antibacterial agents, deodorizers, fragrances, etc. These may be used alone or in combination of two or more. In addition to the above-mentioned components, other components may include repellents (water repellents and / or oil repellents, etc.), dispersants, texture modifiers, softeners, flame retardants, paint fixatives, wrinkle inhibitors, drying speed regulators, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, insect repellents, defoamers, shrinkage inhibitors, anti-wrinkle agents when washed, shape retention agents, drape retention agents, ironing improvers, whitening agents, whitening agents, fabric softening clay, dye transfer inhibitors such as polyvinylpyrrolidone, polymer dispersants, stain release agents, scum dispersants, fluorescent whitening agents such as 4,4-bis(2-sulfostyryl)biphenyl disodium (Tinopal CBS-X manufactured by Chiba Specialty Chemicals), dye fixatives, and anti-fading agents such as 1,4-bis(3-aminopropyl)piperazine. The following may be blended: stain removers, stain removers, enzymes such as cellulase, amylase, protease, lipase, and keratinase as fiber surface modifiers; foam inhibitors; and agents capable of imparting the texture and functionality of silk, such as moisture absorption and release. These include silk protein powder, surface-modified products, or emulsified dispersions thereof (e.g., K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemicals), hydrolyzed silk liquid (Jomo), Silkgen G Soluble S (Ichimaru Falcos)), and stain-preventing agents (e.g., nonionic polymer compounds composed of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units (e.g., FR627 manufactured by GOO Chemical Industry Co., Ltd.), SRC-1 manufactured by Clariant Japan, etc.). These may be used alone or in combination of two or more. The components may be appropriately determined depending on the intended use of the repellent.

[0211] [Amount of Other Components] The amount of each or the total amount of the other components may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the hydrocarbon group-containing polymer, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0212] <Pulp Composition> The pulp composition according to the present disclosure includes a hydrocarbon group-containing polymer and a pulp base material. The pulp composition according to the present disclosure may have excellent oil resistance.

[0213] The pulp composition of the present disclosure is obtained by adding a hydrocarbon group-containing polymer to a pulp base material. The pulp composition may be obtained by treating the pulp base material with a repellent containing the hydrocarbon group-containing polymer, and the amount of repellent added and the composition of the repellent may be adjusted so that each component is present in a desired amount. Each component that may be contained in the repellent may be added to the pulp composition as a separate additive.

[0214] The pulp composition of the present disclosure may not contain any compound selected from the group consisting of a compound having a fluoroalkyl group having 8 or more carbon atoms, a compound having a perfluoroalkyl group having 8 or more carbon atoms, a compound having a fluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group, a compound having a fluoroalkyl group, and a compound having a fluorine atom. The pulp composition of the present disclosure can impart liquid repellency to a substrate even without containing these fluorine compounds.

[0215] The pH of the pulp composition may be 3 to 10, for example 5 to 9, particularly 6 to 8, and the amount of each component may be adjusted to achieve such a pH.

[0216] [Pulp Base Material] The pulp composition includes a pulp base material. The pulp base material is made of pulp, and the pulp may be wood pulp, non-wood pulp, recycled paper pulp, or the like.

[0217] [Wood Pulp] Wood pulp includes softwood kraft pulp obtained from species such as Abies and Pinus, and hardwood kraft pulp obtained from species such as Acacia, Eucalyptus, Beech, and Populus (e.g., poplar). Examples of softwood kraft pulp include unbleached softwood kraft pulp (NUKP), bleached softwood pulp (NBKP), semi-bleached softwood kraft pulp (NSBKP), and softwood sulfite pulp. Examples of hardwood kraft pulp include unbleached hardwood kraft pulp (LUKP), bleached hardwood kraft pulp (LBKP), semi-bleached hardwood kraft pulp (LSBKP), and hardwood sulfite pulp. The pulps used may be used alone or in combination. In addition to kraft pulp, there are also softwood kraft pulp and hardwood kraft pulp, as well as mechanical pulps such as stone ground pulp (SGP), pressurized stone ground pulp (PGW), refiner ground pulp (RGP), thermoground pulp (TGP), chemiground pulp (CGP), groundwood pulp (GP), thermomechanical pulp (TMP), etc. Furthermore, waste paper pulp includes disintegrated waste paper pulp, disintegrated and deinked waste paper pulp, or disintegrated, deinked and bleached waste paper pulp, which are produced from brown waste paper, recycled kraft envelope paper, recycled magazine paper, recycled newspaper paper, recycled flyer paper, recycled office paper, recycled corrugated cardboard paper, white recycled paper, Kent recycled paper, imitation recycled paper, recycled land paper, etc.

[0218] [Non-wood Pulp] Examples of non-wood pulp include pulp obtained from bagasse, kenaf, bamboo, linter, cotton, linen, hemp, ramie, straw, esparto, Manila hemp, sisal hemp, jute, flax, ganpi, mitsumata, kozo, etc.

[0219] [Pulp fiber length] From the viewpoint of improving oil resistance, the average fiber length of the pulp is preferably 0.1 mm or more, more preferably 0.3 mm or more, and even more preferably 0.5 mm or more, and from the viewpoint of ease of production, it is preferably 5.0 mm or less, more preferably 4.0 mm or less, even more preferably 3.0 mm or less, particularly preferably 2.0 mm or less, and most preferably 1.2 mm or less.

[0220] [Pulp Fiber Width] From the viewpoint of improving oil resistance, the average fiber diameter of the pulp is preferably 5 μm or more, more preferably 10 μm or more, even more preferably 15 μm or more, and is preferably 50 μm or less, more preferably 40 μm or less, even more preferably 30 μm or less.

[0221] [Form of Pulp Base Material] The form of the pulp base material when the hydrocarbon group-containing polymer is added may be pulp alone, a pulp slurry, a pulp product, or the like. Specific examples include pulp such as bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulp such as groundwood pulp, mechanical pulp or thermomechanical pulp; pulp slurries containing the above pulp; and pulp products such as paper, paper containers, and pulp molded products.

[0222] [Amount of Pulp Base Material] The amount of the pulp base material in the pulp composition may be 0.1% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 50% by weight or more, 75% by weight or more, or 90% by weight or more, and may be 99% by weight or less, 75% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, 4% by weight or less, or 3% by weight or less. When the pulp composition is prepared by internal addition, the amount of the pulp base material in the pulp composition may be 30% by weight or less, and when the pulp composition is prepared by external addition, the amount of the pulp base material in the pulp composition may be 75% by weight or more.

[0223] The amount of the pulp base material may be 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, 90% by weight or more, 95% by weight or more, or 99% by weight or more in the pulp composition excluding the liquid medium, and may be 99.9% by weight or less, 95% by weight or less, 90% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, or 55% by weight or less.

[0224] [Liquid Medium] The pulp composition may contain a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent, and is typically an aqueous medium (water or a mixture of water and an organic solvent), particularly water. The liquid medium may also contain a liquid medium derived from a repellent.

[0225] [Amount of Liquid Medium] The amount of the liquid medium in the pulp composition may be 0.1 wt% or more, 0.5 wt% or more, 1 wt% or more, 3 wt% or more, 5 wt% or more, 10 wt% or more, 20 wt% or more, 30 wt% or more, 50 wt% or more, 75 wt% or more, 90 wt% or more, or 95 wt% or more, and may be 99 wt% or less, 75 wt% or less, 50 wt% or less, 40 wt% or less, 30 wt% or less, 20 wt% or less, 10 wt% or less, 5 wt% or less, 4 wt% or less, or 3 wt% or less. Typically, when the pulp composition is prepared by internal addition, the amount of the liquid medium in the pulp composition is 50 wt% or more, particularly 90 wt% or more, and when the pulp composition is prepared by external addition, the amount of the liquid medium in the pulp composition may be 30 wt% or less, particularly 10 wt% or less.

[0226] [Hydrocarbon Group-Containing Polymer] The pulp composition contains a hydrocarbon group-containing polymer. For details of the hydrocarbon group-containing polymer, the explanation of the hydrocarbon group-containing polymer in the above <Repellent Agent> is incorporated herein by reference.

[0227] [Amount of Hydrocarbon Group-Containing Polymer] The amount of the hydrocarbon group-containing polymer, relative to the pulp base material, may be 0.01% by weight or more, 0.03% by weight or more, 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 is preferably 0.03% by weight or more, for example 0.5% by weight or more, and may be 25% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, for example 15% by weight or less or 5.0% by weight or less, and preferably 3.0% by weight or less.

[0228] The hydrocarbon group-containing polymer may be added externally to the surface of a pulp substrate (e.g., a pulp product such as paper, a paper container, or a pulp molded product), and the amount of the hydrocarbon group-containing polymer contained in the coating layer formed by the external addition treatment is 0.01 g / m ２ Above, 0.03g / m ２ Above, 0.05g / m ２ Above, 0.1g / m ２ Above, 0.3g / m ２ Above, 0.5g / m ２ or more, or 1.0 g / m ２ or more, and ２ Below, 4.0g / m ２ Below, 3.0g / m ２ Below, 2.0g / m ２ Below, 1.0g / m ２ Below, 0.5g / m ２ Below, 0.3g / m ２ or less, or 0.1 g / m ２ It may be the following:

[0229] [Lignin Compound] The pulp composition preferably contains a lignin compound. For details of the lignin compound, the explanation of the lignin compound in <Repellent Agent> is incorporated herein by reference.

[0230] [Amount of lignin compound] The amount of lignin compound relative to the pulp base material may be 0.1 wt% or more, 0.3 wt% or more, 0.5 wt% or more, 0.75 wt% or more, 1.0 wt% or more, 2.0 wt% or more, or 3.0 wt% or more, and may be 10 wt% or less, 7.5 wt% or less, 5.0 wt% or less, 4.0 wt% or less, 3.0 wt% or less, 2.0 wt% or less, 1.0 wt% or less, 0.75 wt% or less, or 0.5 wt% or less, preferably 5.0 wt% or less, more preferably 3.0 wt% or less.

[0231] [Dispersant] The pulp composition may contain a dispersant. For details of the dispersant, the description of the dispersant in <Repellent> is incorporated herein by reference.

[0232] [Amount of Dispersant] The amount of dispersant may be 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more, and may be 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, preferably 5.0% by weight or less, more preferably 3.0% by weight or less, based on the pulp base material.

[0233] [Paper Strength Agent] The pulp composition may contain a paper strength agent. Examples of the paper strength agent include polyacrylamide-based paper strength agents such as cationic polyacrylamide, anionic polyacrylamide, and amphoteric polyacrylamide; polysaccharide-based paper strength agents such as starch, enzyme-modified starch, thermochemically modified starch, oxidized starch, esterified starch, etherified starch (e.g., hydroxyethylated starch), aldehyde-modified starch, cationized starch, starch, xanthan gum, karaya gum, welan gum, guar gum, pectin, tamarind gum, carrageenan, chitosan, gum arabic, locust bean gum, cellulose, alginic acid, agar, dextran, cellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, chitin nanofiber, cellulose nanofiber, and pullulan, and modified polysaccharides thereof (e.g., modified polysaccharides into which a hydroxyl group or a cationic group has been introduced); Polyamide-based paper strength agents such as polyamide resins, polyamine resins, polyamide-polyamine resins, polyamide-epichlorohydrin resins, polyamide-polyamine-epichlorohydrin resins, polyamide-polyurea-formaldehyde resins, and epoxidized polyamide resins; urea / melamine-based paper strength agents such as urea resins, melamine resins, urea-formaldehyde resins, and melamine-formaldehyde resins; polyvinyl alcohol-based paper strength agents such as polyvinyl alcohol, fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, cation-modified polyvinyl alcohol, and terminally alkyl-modified polyvinyl alcohol; styrene-butadiene copolymers, polyvinyl acetate, vinyl chloride-vinyl acetate copolymers, polyvinyl chloride, polyvinylidene chloride, polyacrylic acid esters, fatty acid diamides, polyethyleneimine resins, and ketone aldehyde resins. The paper strength agent in the present disclosure is preferably a polyacrylamide-based paper strength agent, a polysaccharide-based paper strength agent, or a polyamide-based paper strength agent.

[0234] [Amount of Paper Strength Agent] The amount of the paper strength agent may be 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more, and may be 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, and is preferably 5.0% by weight or less, based on the pulp.

[0235] [Sizing Agent] The pulp composition may contain a sizing agent. Examples of the sizing agent include cationic sizing agents, anionic sizing agents, neutral sizing agents, and amphoteric sizing agents, such as rosin-based sizing agents (e.g., acidic rosin-based sizing agents, neutral rosin-based sizing agents), alkyl ketene dimers, and alkenyl succinic anhydrides.

[0236] [Amount of Sizing Agent] The amount of sizing agent may be 0.1% by weight or more, 0.2% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more, and may be 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, based on the pulp.

[0237] [Other Additives] In addition to the above, the pulp composition may contain other additives such as known paper co-agents used in the production of pulp products, such as fixing agents (water-soluble aluminum compounds such as aluminum sulfate and polyaluminum chloride), coagulants / flocculants (polyamine resins, etc.), retention aids (polyacrylamide resins, etc.), organic acids (formic acid, acetic acid, etc.), dyes, slime control agents, and antifoaming agents.

[0238] [Amount of Other Additives] The amount of other additives may be 0.01% by weight or more, 0.1% by weight or more, 1% by weight or more, 3% by weight or more, or 5% by weight or more, and may be 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, 3% by weight or less, or 1% by weight or less, based on the pulp base material.

[0239] <Product Manufacturing Method> The product manufacturing method of the present disclosure may include a step of treating a substrate with the repellent agent of the present disclosure as a treatment agent.

[0240] The substrate to be treated with the treatment agent of the present disclosure is not limited, but is preferably a fibrous substrate, particularly a textile substrate or a pulp substrate, and is particularly preferably a pulp substrate.

[0241] Examples of fiber substrates include natural fibers of animal or plant origin such as cotton, hemp, wool, silk, etc., synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polypropylene, etc., semi-synthetic fibers such as rayon, acetate, etc., inorganic fibers such as glass fiber, carbon fiber, asbestos fiber, etc., or mixtures of these fibers. Fiber products include woven fabrics, knitted fabrics, nonwoven fabrics, cloth in the form of clothing (for example, water-repellent clothing, e.g., raincoats), and carpets, but the treatment may also be applied to fibers, yarns, and intermediate fiber products (for example, slivers or rovings) in a state prior to being made into cloth.

[0242] Substrates that can be treated with the treatment agent of the present disclosure are not limited to fibrous substrates, but also include stone, filters (e.g., electrostatic filters), dust masks, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster.

[0243] When the substrate is glass, the produced glass product may be an optical component. A layer (or film), such as a hard coat layer or an anti-reflection layer, may be formed on the surface (outermost layer) of the glass substrate. The anti-reflection layer may be either a single-layer anti-reflection layer or a multi-layer anti-reflection layer. Examples of inorganic substances that can be used for the anti-reflection layer include SiO ２ , SiO, ZrO ２ , TiO ２ , TiO, Ti ２ O ３ , Ti ２ O ５ , Al ２ O ３ , Ta ２ O５ , CeO ２ , MgO, Y ２ O ３ , SnO ２ , MgF ２ , W.O. ３ These inorganic substances may be used alone or in combination of two or more (for example, as a mixture). When a multi-layer antireflection layer is formed, the outermost layer may contain SiO ２ and / or SiO is preferably used. When the article to be manufactured is an optical glass component for a touch panel, a transparent electrode, for example, a thin film using indium tin oxide (ITO) or indium zinc oxide, may be provided on a portion of the surface of the substrate (glass). Furthermore, the substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomization film layer, a hard coating film layer, a polarizing film, a phase difference film, a liquid crystal display module, or the like, depending on its specific specifications.

[0244] [Method for producing pulp product] The pulp product (paper product) in the present disclosure can be obtained by treating a pulp base material with a repellent containing a hydrocarbon group-containing polymer to obtain a pulp composition, and then subjecting the pulp composition to treatment steps such as drying, heating, molding, etc. as necessary. The pulp product may be an oil-resistant pulp product that has been treated with an oil-proofing agent.

[0245] The repellent agent of the present disclosure can be applied to a pulp substrate as a treatment agent (particularly a surface treatment agent) by a conventionally known method. The treatment method may involve dispersing and diluting the repellent agent of the present disclosure in an organic solvent or water, as necessary, and applying it to the interior and / or surface of the pulp substrate by a known method such as dip coating, spray coating, or foam coating, followed by drying. The dilution ratio may be varied as appropriate depending on the concentration and application of the repellent agent, but may be 3 to 2000 times, for example, 10 to 100 times. After drying, a pulp product is obtained to which the solid components of the repellent are attached. If necessary, the repellent agent may be applied together with an appropriate crosslinking agent, followed by curing.

[0246] The repellent agent can be applied to the pulp substrate by any of the known methods for treating a pulp substrate with a liquid. The pulp substrate may be immersed in the repellent agent, the pulp substrate and the repellent agent may be mixed, or the solution may be applied or sprayed onto the pulp substrate. The treated pulp substrate is preferably dried and cured by heating to develop liquid repellency. The heating temperature may be, for example, 100°C to 200°C, 100°C to 170°C, or 100°C to 120°C. In the present disclosure, the heating time may be 5 seconds to 60 minutes, for example, 30 seconds to 3 minutes.

[0247] Pulp substrate treatment methods can include internal treatment methods in which a repellent is added to the pulp substrate (e.g., in the form of pulp slurry) before papermaking, or external treatment methods in which a repellent is applied to the pulp substrate (e.g., pulp product) after papermaking. Examples of internal treatment methods include mixing and immersion, which may include a step of adding a repellent to the pulp slurry and stirring and mixing it. Examples of external treatment methods include spraying, coating, immersion, and foam application, and specific examples include pond-type two-roll size presses, gate-roll type, and rod-metering size presses. The treatment can be either external or internal. For example, when the pulp substrate is paper, the repellent can be applied to the paper, or the solution can be attached or sprayed onto the paper, or the repellent can be mixed with the pulp slurry before papermaking. When the pulp substrate is a fibrous material, treatment methods include padding, immersion, spraying, and coating. Examples of padding treatments include methods using padding devices described on pages 396-397 of "Textile Dyeing and Processing Dictionary" (published by Nikkan Kogyo Shimbun, 1963) and pages 256-260 of "Color Dyeing Chemistry III" (published by Jikkyo Publishing Co., Ltd., 1975). Examples of coating treatments include methods using coating machines described on pages 473-477 of "Dyeing and Finishing Equipment Directory" (published by Sen-sha, 1981). Examples of immersion treatments include methods using batch dyeing machines described on pages 196-247 of "Dyeing and Finishing Equipment Directory" (published by Sen-sha, 1981). Examples of suitable dyeing machines include liquid jet dyeing machines, air jet dyeing machines, drum dyeing machines, winch dyeing machines, washer dyeing machines, and cheese dyeing machines. Examples of spray treatments include methods using air sprayers that spray the treatment solution in a mist using compressed air, and hydraulic atomization air sprayers.

[0248] The treatment method may be an internal addition treatment in which a repellent is added to a pulp slurry before papermaking. The internal addition treatment may include filling the pulp slurry into a mold and allowing a liquid medium to permeate out of the mold to form pulp. For example, the internal addition treatment may include one or more of the following steps: adding a repellent to the pulp slurry and stirring and mixing it; suction-dehydrating the pulp composition prepared in the above step through a mesh of a predetermined shape to deposit the pulp composition and form a molded pulp product intermediate; and molding and drying the molded pulp product intermediate in a heated mold to obtain a molded pulp product. The treated paper may be simply dried at room temperature or at an elevated temperature, and then optionally subjected to a heat treatment depending on the paper's properties. The heat treatment temperature may be 150°C or higher, 180°C or higher, or 210°C or higher, and 300°C or lower, 250°C or lower, or 200°C or lower, and particularly 80°C to 180°C. Heat treatment within this temperature range can exhibit excellent oil resistance, etc. The internally treated pulp base material may be treated with a repellent by external addition, and further a hydrocarbon group-containing polymer or a repellent may be attached to the surface.

[0249] The treatment method may be an external addition treatment in which a repellent agent is applied to the pulp base material after papermaking. Size presses for external addition treatment can also be divided into the following categories based on the application method. One application method is the so-called pond-type two-roll size press, in which a coating liquid (size liquid) is supplied to the nip formed by passing paper between two rubber rolls, creating a coating liquid pool called a pond, and the paper is passed through this coating liquid pool to apply the size liquid to both sides of the paper. Other application methods include the gate roll type, in which the size liquid is applied using a surface transfer method, and the rod metering size press. In the pond-type two-roll size press, the size liquid easily penetrates into the paper, while in the surface transfer type, the size liquid components tend to remain on the paper surface. In the surface transfer type, the coating layer tends to remain on the paper surface compared to the pond-type two-roll size press, and a larger coating layer is formed on the surface than in the pond-type two-roll size press. In the present disclosure, performance can be imparted to paper even when the former pond-type two-roll size press is used. Papers treated in this way may exhibit excellent oil resistance etc., after simple drying at room temperature or at elevated temperatures, optionally followed by a heat treatment which may range in temperature up to 300°C, for example up to 200°C, especially between 80°C and 180°C, depending on the properties of the paper.

[0250] Specific examples of pulp products include paper, paper containers, pulp molded products, food packaging materials, food containers, gypsum board base paper, coated base paper, medium-quality paper, general liners and corrugating media, neutral white roll paper, neutral liners, rust-proof liners and metal interleaving paper, kraft paper, neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper, and neutral information paper, etc. Suitable examples of pulp products include food packaging materials and food containers, such as pulp products for food contact applications, particularly pulp molded products for food contact applications.

[0251] Although the embodiments have been described above, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims.

[0252] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to these examples.

[0253] <Test Method> The test procedure is as follows.

[0254] [High-temperature oil resistance] 100 ml of an evaluation liquid (corn oil) at 65°C or 80°C was poured into a pulp molded product formed into a container, and after leaving it to stand for 45 minutes or 30 minutes, the evaluation liquid was discarded, and the degree of penetration of the evaluation liquid into the pulp molded product (container) was visually evaluated according to the following criteria: 4: Almost no oil stains were observed on the inside of the container bottom; 3: No oil stains were observed on the outside of the container bottom; 2: Oil stains were observed over less than 5% of the outside area of ​​the container bottom; 1: Oil stains were observed over 5% or more but less than 50% of the outside area of ​​the container bottom; 0: Oil stains were observed over 50% or more of the outside area of ​​the container bottom.

[0255] [High-temperature water resistance] 100 ml of an evaluation liquid (water) at 100°C was poured into a pulp molded product formed into a container, and after leaving it to stand for 30 minutes, the evaluation liquid was discarded, and the degree of penetration of the evaluation liquid into the pulp molded product (container) was visually evaluated according to the following criteria: 4: Almost no liquid staining was observed inside the bottom of the container 3: No liquid staining was observed outside the bottom of the container 2: Liquid staining was observed over less than 5% of the outer area of ​​the bottom of the container 1: Liquid staining was observed over 5% or more but less than 50% of the outer area of ​​the bottom of the container 0: Liquid staining was observed over 50% or more of the outer area of ​​the bottom of the container

[0256] [Product stability] 40 g of the liquid repellent was placed in a 50 ml glass bottle and left to stand at 20°C, and the stability was evaluated visually according to the following criteria: ◯: No settling or separation for 4 weeks. △: No settling or separation for 1 week, but settling or separation occurs within 4 weeks. ×: Settling or separation occurs within 1 week.

[0257] Synthesis Example 1: A 1-liter plastic container was charged with 97 parts of stearamidoethyl acrylate, 3 parts of hydroxybutyl acrylate (HBA), 370 parts of pure water, 3 parts of sodium lignin sulfonate, and 12 parts of polyoxyethylene alkyl ether. The mixture was heated to 80°C and then ultrasonically emulsified and dispersed for 15 minutes. The emulsified dispersion was transferred to a 1000 cc four-neck flask equipped with a nitrogen inlet tube, thermometer, stirring rod, and reflux condenser. After nitrogen substitution, 1 part of ammonium persulfate was added, and the mixture was allowed to react at 60°C for 4 hours to obtain an aqueous dispersion of a polymer. Pure water was then added to prepare an aqueous dispersion (oil-resistant agent) with a solids concentration of 20% by weight.

[0258] Synthesis Example 2 A 1 L plastic container was charged with 100 parts of stearamidoethyl acrylate, 370 parts of pure water, 3 parts of sodium lignosulfonate, and 12 parts of polyoxyethylene alkyl ether, and an aqueous dispersion was prepared in the same manner as in Synthesis Example 1.

[0259] Synthesis Example 3 A 1 L plastic container was charged with 97 parts of stearamidoethyl acrylate, 3 parts of hydroxybutyl acrylate (HBA), 370 parts of pure water, and 12 parts of polyoxyethylene alkyl ether, and an aqueous dispersion was prepared in the same manner as in Synthesis Example 1.

[0260] Synthesis Example 4 A 1 L plastic container was charged with 100 parts of stearic acid amide ethyl acrylate, 370 parts of pure water, and 12 parts of polyoxyethylene alkyl ether, and an aqueous dispersion was prepared in the same manner as in Synthesis Example 1.

[0261] Synthesis Example 5: A 1-L plastic container was charged with 97 parts of stearamidoethyl acrylate, 3 parts of hydroxybutyl acrylate (HBA), 370 parts of pure water, and 12 parts of polyoxyethylene alkyl ether, and the mixture was heated to 80°C and then ultrasonically emulsified and dispersed for 15 minutes. The emulsified dispersion was transferred to a 1,000 cc four-neck flask equipped with a nitrogen inlet tube, a thermometer, a stirring rod, and a reflux condenser. After purging with nitrogen, 1 part of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added, and the mixture was allowed to react at 60°C for 4 hours to obtain an aqueous dispersion of a polymer. Pure water was then added to prepare an aqueous dispersion with a solids concentration of 20% by weight.

[0262] Synthesis Example 6 A 1 L plastic container was charged with 100 parts of stearamidoethyl acrylate, 370 parts of pure water, 0.8 parts of acetic acid, and 12 parts of polyoxyethylene alkyl ether, and an aqueous dispersion was prepared in the same manner as in Synthesis Example 5.

[0263] Synthesis Example 7 A 1 L plastic container was charged with 100 parts of stearic acid amide ethyl acrylate, 370 parts of pure water, 0.8 parts of acetic acid, 7 parts of alkylbis(2-hydroxyalkyl)methylammonium chloride, and 3 parts of polyoxyethylene alkyl ether, and an aqueous dispersion was prepared in the same manner as in Synthesis Example 5.

[0264] Synthesis Example 8 A 1 L plastic container was charged with 93 parts of stearamidoethyl acrylate, 7 parts of hydroxybutyl acrylate (HBA), 370 parts of pure water, 3 parts of sodium ligninsulfonate, and 12 parts of polyoxyethylene alkyl ether, and an aqueous dispersion was prepared in the same manner as in Synthesis Example 1.

[0265] Synthesis Example 9 A 1 L plastic container was charged with 96 parts of stearic acid amide ethyl acrylate, 3 parts of hydroxybutyl acrylate (HBA), 1 part of dimethylaminoethyl methacrylate (DM), 0.5 parts of acetic acid, 370 parts of pure water, 3 parts of sodium ligninsulfonate, and 12 parts of polyoxyethylene alkyl ether, and an aqueous dispersion was prepared in the same manner as in Synthesis Example 1.

[0266] Synthesis Example 10: A 1-L plastic container was charged with 100 parts of stearamidoethyl acrylate, 10 parts of tripropylene glycol, 360 parts of pure water, 13 parts of polyoxyethylene alkyl ether, and 2 parts of lauric acid. The mixture was heated to 80°C and then ultrasonically emulsified and dispersed for 15 minutes. The emulsified dispersion was transferred to a 1000 cc four-neck flask equipped with a nitrogen inlet tube, a thermometer, a stirring rod, and a reflux condenser. After nitrogen substitution, 1 part of ammonium persulfate was added and the mixture was allowed to react at 60°C for 4 hours to obtain an aqueous dispersion of a polymer. 3 parts of sodium lignosulfonate were added to the emulsion and the mixture was stirred and dispersed. Pure water was then added to prepare an aqueous dispersion with a solids concentration of 20% by weight. Synthesis Example 11: A 1 L plastic container was charged with 100 parts of stearamidoethyl acrylate, 10 parts of tripropylene glycol, 360 parts of pure water, 13 parts of polyoxyethylene alkyl ether, and 2 parts of sorbitan monostearate (NIKKOL SS-10V, manufactured by Nikko Chemicals). The mixture was heated to 80°C and then ultrasonically emulsified and dispersed for 15 minutes. The emulsified dispersion was transferred to a 1000 cc four-neck flask equipped with a nitrogen inlet tube, thermometer, stirring rod, and reflux condenser. After nitrogen substitution, 1 part of ammonium persulfate was added and the mixture was allowed to react at 60°C for 4 hours to obtain an aqueous dispersion of a polymer. 3 parts of sodium lignosulfonate were added to the emulsion and the mixture was stirred and dispersed. Pure water was then added to prepare an aqueous dispersion with a solids concentration of 20% by weight. Synthesis Example 12: A 1 L plastic container was charged with 100 parts of stearamidoethyl acrylate, 10 parts of tripropylene glycol, 360 parts of pure water, 13 parts of polyoxyethylene alkyl ether, and 2 parts of sorbitan tristearate (NIKKOL SS-30V, manufactured by Nikko Chemicals), heated to 80°C, and then ultrasonically emulsified and dispersed for 15 minutes. The emulsified dispersion was transferred to a 1000 cc four-neck flask equipped with a nitrogen inlet tube, thermometer, stirring rod, and reflux condenser. After nitrogen substitution, 1 part of ammonium persulfate was added, and the mixture was allowed to react at 60°C for 4 hours to obtain an aqueous dispersion of a polymer. 3 parts of sodium lignosulfonate were added to the emulsion, and the mixture was stirred and dispersed. Pure water was then added to prepare an aqueous dispersion with a solids concentration of 20% by weight.

[0267] Comparative Synthesis Example 1 A 1 L plastic container was charged with 90 parts of stearamidoethyl acrylate, 10 parts of hydroxybutyl acrylate (HBA), 370 parts of pure water, 3 parts of sodium ligninsulfonate, and 12 parts of polyoxyethylene alkyl ether, and an aqueous dispersion was prepared in the same manner as in Synthesis Example 1.

[0268] Comparative Synthesis Example 2 A 1 L plastic container was charged with 90 parts of stearamidoethyl acrylate, 7 parts of hydroxybutyl acrylate (HBA), 3 parts of dimethylaminoethyl methacrylate (DM), 0.5 parts of acetic acid, 370 parts of pure water, 3 parts of sodium ligninsulfonate, and 12 parts of polyoxyethylene alkyl ether, and an aqueous dispersion was prepared in the same manner as in Synthesis Example 1.

[0269] Comparative Synthesis Example 3 A 1 L plastic container was charged with 90 parts of stearamidoethyl acrylate, 7 parts of hydroxybutyl acrylate (HBA), 3 parts of dimethylaminoethyl methacrylate (DM), 0.5 parts of acetic acid, 370 parts of pure water, 7 parts of alkylbis(2-hydroxyalkyl)methylammonium chloride, and 3 parts of polyoxyethylene alkyl ether, and an aqueous dispersion was prepared in the same manner as in Synthesis Example 5.

[0270] Comparative Synthesis Example 4 A 1 L plastic container was charged with 90 parts of stearamidoethyl acrylate, 7 parts of hydroxybutyl acrylate (HBA), 3 parts of dimethylaminoethyl methacrylate (DM), 0.5 parts of acetic acid, 370 parts of pure water, and 12 parts of polyoxyethylene alkyl ether, and an aqueous dispersion was prepared in the same manner as in Synthesis Example 5.

[0271] Example 1 To a 550 cc (Canadian freeness) container, 2000 g of a 0.5 wt % aqueous dispersion of a mixture of 70 parts of beaten bleached hardwood kraft pulp and 30 parts of bleached softwood kraft pulp was added with stirring, and then 2 g of the aqueous dispersion of Synthesis Example 1 diluted with water to a solids content of 10% was added and stirring was continued for 1 minute. Next, 0.16 g of a cationic polyamine (Hercobond (registered trademark) 6950 manufactured by Solenis) diluted to a solids content of 10% was added and stirring was continued for 1 minute or 120 minutes.

[0272] The pulp slurry was placed in a metal tank. A metal pulp mold mold with numerous suction holes was placed at the bottom of the tank, with a mesh-like body placed on top. A vacuum pump was used to suck and dehydrate the pulp-containing aqueous composition through the pulp mold mold and mesh-like body from the side opposite the mesh-like body of the pulp mold mold, depositing the solids (pulp, etc.) contained in the pulp-containing aqueous composition on the mesh-like body to obtain a pulp-molded intermediate. The obtained pulp-molded intermediate was then dried by applying pressure from above and below using a male-female metal mold heated to 60 to 200°C. This produced a pulp-molded product molded into the shape of a container. The content ratio of each component relative to the pulp in the obtained pulp-molded product, as well as the high-temperature oil and water resistance and product stability, were evaluated, and the results are shown in Table 1.

[0273] Example 2 An experiment was conducted in the same manner as in Example 1, except that 1.5 g of the aqueous dispersion from Synthesis Example 1 diluted with water to a 10% solids content was added, and that after adding and stirring a cationic polyamine (Hercobond (registered trademark) 6950 manufactured by Solenis), 0.8 g of amphoteric polyacrylamide (product name: Hermide T2, manufactured by Harima Chemicals) diluted with water to a 10% solids content was added and stirred for 1 minute, and then 0.8 g of amphoteric polyacrylamide (product name: Hermide KS38, manufactured by Harima Chemicals) diluted with water to a 10% solids content was added and stirred for 1 minute. The content ratio of each component relative to the pulp in the obtained pulp molded product, as well as the high-temperature oil and water resistance and product stability were evaluated, and the results are shown in Table 1.

[0274] Example 3 An experiment was conducted in the same manner as in Example 1, except that 1.5 g of the aqueous dispersion from Synthesis Example 1 diluted with water to a 10% solids content was added, 0.8 g of amphoteric polyacrylamide (product name: HARAMID T2, manufactured by Harima Chemicals) diluted with water to a 10% solids content was added and stirred for 1 minute, 0.8 g of amphoteric polyacrylamide (product name: HARAMID KS38, manufactured by Harima Chemicals) diluted with water to a 10% solids content was added and stirred for 1 minute, and 0.3 g of aluminum sulfate diluted with water to a 1% solids content was added and stirred for 1 minute. The content ratio of each component relative to the pulp in the obtained pulp-molded product, as well as the high-temperature oil and water resistance and product stability were evaluated, and the results are shown in Table 1.

[0275] Example 4 An experiment was carried out in the same manner as in Example 3, except that 0.3 g of a 5% solids aqueous solution of alkyl ketene dimer (AKD) (Hercon (registered trademark) 79 manufactured by Solenis) was added as a sizing agent and stirred for 1 minute. The content ratio of each component relative to the pulp in the obtained pulp-molded product, as well as the high-temperature oil resistance and high-temperature water resistance were evaluated, and the results are shown in Table 1.

[0276] Example 5 An experiment was carried out in the same manner as in Example 1, except that 2.0 g of the aqueous dispersion of Synthesis Example 2 diluted with water to a solids content of 10% was added. The content ratio of each component relative to the pulp in the obtained pulp molded product, as well as the high-temperature oil resistance and high-temperature water resistance were evaluated. The results are shown in Table 1.

[0277] Example 6 An experiment was carried out in the same manner as in Example 2, except that 1.2 g of the aqueous dispersion of Synthesis Example 2 diluted with water to a solids content of 10% was added. The content ratio of each component relative to the pulp in the obtained pulp molded product, as well as the high-temperature oil resistance and high-temperature water resistance were evaluated. The results are shown in Table 1.

[0278] Example 7 An experiment was carried out in the same manner as in Example 3, except that 1.2 g of the aqueous dispersion of Synthesis Example 2 diluted with water to a solids content of 10% was added. The content ratio of each component relative to the pulp in the obtained pulp molded product, as well as the high-temperature oil resistance and high-temperature water resistance were evaluated, and the results are shown in Table 1.

[0279] Example 8 An experiment was carried out in the same manner as in Example 4, except that 1.2 g of the aqueous dispersion of Synthesis Example 2 diluted with water to a solids content of 10% was added. The content ratio of each component relative to the pulp in the obtained pulp molded product, as well as the high-temperature oil resistance and high-temperature water resistance were evaluated. The results are shown in Table 1.

[0280] Example 9 An experiment was carried out in the same manner as in Example 1, except that the aqueous dispersion of Synthesis Example 3 was added. The content ratio of each component relative to the pulp in the obtained pulp molded product, as well as the high-temperature oil resistance and high-temperature water resistance were evaluated. The results are shown in Table 1.

[0281] Example 10 An experiment was carried out in the same manner as in Example 1, except that the aqueous dispersion of Synthesis Example 4 was added. The content ratio of each component relative to the pulp in the obtained pulp molded product, as well as the high-temperature oil resistance and high-temperature water resistance were evaluated. The results are shown in Table 1.

[0282] Example 11 An experiment was carried out in the same manner as in Example 1, except that the aqueous dispersion of Synthesis Example 5 was added. The content ratio of each component relative to the pulp in the obtained pulp molded product, as well as the high-temperature oil resistance and high-temperature water resistance were evaluated. The results are shown in Table 1.

[0283] Example 12 An experiment was carried out in the same manner as in Example 1, except that the aqueous dispersion of Synthesis Example 6 was added. The content ratio of each component relative to the pulp in the obtained pulp molded product, as well as the high-temperature oil resistance and high-temperature water resistance were evaluated. The results are shown in Table 1.

[0284] Example 13 An experiment was carried out in the same manner as in Example 1, except that the aqueous dispersion of Synthesis Example 7 was added. The content ratio of each component relative to the pulp in the obtained pulp molded product, as well as the high-temperature oil resistance and high-temperature water resistance were evaluated. The results are shown in Table 1.

[0285] Example 14 An experiment was carried out in the same manner as in Example 1, except that the aqueous dispersion of Synthesis Example 8 was added. The content ratio of each component relative to the pulp in the obtained pulp molded product, as well as the high-temperature oil resistance and high-temperature water resistance were evaluated. The results are shown in Table 1.

[0286] Example 15 An experiment was carried out in the same manner as in Example 1, except that the aqueous dispersion of Synthesis Example 9 was added. The content ratio of each component relative to the pulp in the obtained pulp molded product, as well as the high-temperature oil resistance and high-temperature water resistance were evaluated. The results are shown in Table 1.

[0287] Example 16 An experiment was carried out in the same manner as in Example 1, except that 2.0 g of the aqueous dispersion of Synthesis Example 10 diluted with water to a solids content of 10% was added. The content ratio of each component relative to the pulp in the obtained pulp molded product, as well as the high-temperature oil resistance and high-temperature water resistance were evaluated. The results are shown in Table 1.

[0288] Example 17 An experiment was conducted in the same manner as in Example 1, except that a mixture of 70 parts hardwood bleached kraft pulp and 30 parts softwood bleached kraft pulp from Example 1 was replaced with a mixture of 50 parts bamboo bleached kraft pulp and 50 parts bagasse bleached kraft pulp. The results of evaluating the content ratio of each component relative to the pulp, as well as the high-temperature oil resistance and high-temperature water resistance of the resulting molded pulp product, are shown in Table 1. Example 18 An experiment was conducted in the same manner as in Example 1, except that 2.0 g of the aqueous dispersion from Synthesis Example 11 diluted with water to a solids content of 10% was added. The results of evaluating the content ratio of each component relative to the pulp, as well as the high-temperature oil resistance and high-temperature water resistance of the resulting molded pulp product are shown in Table 1. Example 19 An experiment was conducted in the same manner as in Example 1, except that 2.0 g of the aqueous dispersion from Synthesis Example 12 diluted with water to a solids content of 10% was added. The results of evaluating the content ratio of each component relative to the pulp, as well as the high-temperature oil resistance and high-temperature water resistance of the resulting molded pulp product are shown in Table 1.

[0289] Comparative Example 1 An experiment was carried out in the same manner as in Example 1, except that the aqueous dispersion of Comparative Synthesis Example 1 was added. The content ratio of each component relative to the pulp in the obtained pulp molded product, as well as the high-temperature oil resistance and high-temperature water resistance were evaluated. The results are shown in Table 1.

[0290] Comparative Example 2 An experiment was carried out in the same manner as in Example 2, except that the aqueous dispersion of Comparative Synthesis Example 1 was added. The content ratio of each component relative to the pulp in the obtained pulp molded product, as well as the high-temperature oil resistance and high-temperature water resistance were evaluated, and the results are shown in Table 1.

[0291] Comparative Example 3 An experiment was carried out in the same manner as in Example 3, except that the aqueous dispersion of Comparative Synthesis Example 1 was added. The content ratio of each component relative to the pulp in the obtained pulp molded product, as well as the high-temperature oil resistance and high-temperature water resistance were evaluated. The results are shown in Table 1.

[0292] Comparative Example 4 An experiment was carried out in the same manner as in Example 4, except that the aqueous dispersion of Comparative Synthesis Example 1 was added. The content ratio of each component relative to the pulp in the obtained pulp molded product, as well as the high-temperature oil resistance and high-temperature water resistance were evaluated. The results are shown in Table 1.

[0293] Comparative Example 5 An experiment was carried out in the same manner as in Example 6, except that the aqueous dispersion of Comparative Synthesis Example 1 was added. The content ratio of each component relative to the pulp in the obtained pulp molded product, as well as the high-temperature oil resistance and high-temperature water resistance were evaluated. The results are shown in Table 1.

[0294] Comparative Example 6 An experiment was carried out in the same manner as in Example 7, except that the aqueous dispersion of Comparative Synthesis Example 1 was added. The content ratio of each component relative to the pulp in the obtained pulp molded product, as well as the high-temperature oil resistance and high-temperature water resistance were evaluated. The results are shown in Table 1.

[0295] Comparative Example 7 An experiment was carried out in the same manner as in Example 8, except that the aqueous dispersion of Comparative Synthesis Example 1 was added. The content ratio of each component relative to the pulp in the obtained pulp molded product, as well as the high-temperature oil resistance and high-temperature water resistance were evaluated. The results are shown in Table 1.

[0296] Comparative Example 8 An experiment was carried out in the same manner as in Example 1, except that the aqueous dispersion of Comparative Synthesis Example 2 was added. The content ratio of each component relative to the pulp in the obtained pulp molded product, as well as the high-temperature oil resistance and high-temperature water resistance were evaluated, and the results are shown in Table 1.

[0297] Comparative Example 9 An experiment was carried out in the same manner as in Example 1, except that the aqueous dispersion of Comparative Synthesis Example 3 was added. The content ratio of each component relative to the pulp in the obtained pulp molded product, as well as the high-temperature oil resistance and high-temperature water resistance were evaluated. The results are shown in Table 1.

[0298] Comparative Example 10 An experiment was carried out in the same manner as in Example 2, except that the aqueous dispersion of Comparative Synthesis Example 3 was added. The content ratio of each component relative to the pulp in the obtained pulp molded product, as well as the high-temperature oil resistance and high-temperature water resistance were evaluated, and the results are shown in Table 1.

[0299] Comparative Example 11 An experiment was carried out in the same manner as in Example 1, except that the aqueous dispersion of Comparative Synthesis Example 4 was added. The content ratio of each component relative to the pulp in the obtained pulp molded product, as well as the high-temperature oil resistance and high-temperature water resistance were evaluated. The results are shown in Table 1.

[0300]

Claims

1. An oil-resistant agent for pulp containing a hydrocarbon group-containing polymer, wherein the hydrocarbon group-containing polymer has a repeating unit derived from a monomer (a1), and the monomer (a1) is a hydrocarbon group-containing monomer having a hydrocarbon group with 6 to 40 carbon atoms and an NH group-containing group, and the amount of the repeating unit derived from the monomer (a1) is more than 90% by weight based on the polymer, the oil-resistant agent for pulp.

2. The oil-resistant agent for pulp according to claim 1, wherein the hydrocarbon group-containing polymer does not have a fluorine atom.

3. The monomer (a1) is of the formula (a1): CH2=C(-X ａ１ )-C(=O)-Y ａ１１ -Z(-Y ａ１２ -R ａ１ ) ｎ [In the formula, R ａ１ is, independently of one another, a hydrocarbon group having 6 to 40 carbon atoms, X ａ１ is a hydrogen atom, a monovalent organic group or a halogen atom, Y ａ１１ is -O- or -NH-, Y ａ１２ is, independently of one another, a direct bond, or a group composed of at least one selected from -O-, -C(=O)-, -S(=O) ２ -, -NH- or -CH ２ -, Z is a direct bond, or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and n is 1 or 2.], and is a monomer represented by the formula. The oil-resistant agent for pulp according to claim 1 or 2.

4. The oil-resistant agent for pulp according to any one of claims 1 to 3, wherein the amount of the repeating unit derived from the monomer (a1) is more than 97% by weight based on the polymer.

5. The amount of the repeating unit derived from the monomer (b) is 0% by weight or more and less than 7% by weight based on the polymer, and the monomer (b) is a hydrophilic monomer having an oxyalkylene-containing group as a hydrophilic group. The oil-resistant agent for pulp according to any one of claims 1 to 4.

6. The amount of the repeating unit derived from the monomer (c) is 0% by weight or more and less than 3% by weight based on the polymer, and the monomer (c) is an ionic group-containing monomer. The oil-resistant agent for pulp according to any one of claims 1 to 5.

7. The oil-resistant agent for pulp according to any one of claims 1 to 6, wherein the hydrocarbon group-containing polymer is a polymer obtained by emulsion polymerization.

8. The oil-resistant agent for pulp according to any one of claims 1 to 7, containing a dispersant.

9. The oil-resistant agent for pulp according to any one of claims 1 to 8, containing an anionic dispersant.

10. The oil-resistant agent for pulp according to any one of claims 1 to 9, containing a lignin compound.

11. The oil-resistant agent for pulp according to any one of claims 1 to 10, containing an aqueous medium.

12. Y ａ１２ The oil-resistant agent for pulp according to claim 3, wherein Y is -NH-C(=O)-, -C(=O)-NH-, -O-C(=O)-NH-, -NH-C(=O)-O- or -NH-C(=O)-NH-.

13. A pulp composition containing a pulp base material and the oil-resistant agent for pulp according to any one of claims 1 to 12.

14. The pulp composition according to claim 13, containing at least one pulp additive selected from the group consisting of a sizing agent, a paper strength agent, and a fixing agent.

15. An oil-resistant pulp product obtained by adhering the hydrocarbon group-containing polymer in the oil-resistant agent for pulp according to any one of claims 1 to 12 to a pulp base material.

16. The oil-resistant pulp product according to claim 15, which is a pulp molded article.

17. The oil-resistant pulp product according to claim 15 or 16, which is a food packaging material or a food container.

18. A method for manufacturing an oil-resistant pulp product, comprising a step of treating a pulp base material by external addition treatment or internal addition treatment with the oil-resistant agent according to any one of claims 1 to 12.

19. The method for manufacturing an oil-resistant pulp product according to claim 18, comprising filling the oil-resistant agent and a pulp slurry into a mold and permeating a liquid medium outside the mold to form the pulp.

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