Oil-resistant agent composition

Abstract

This invention provides an oil-resistant agent composition containing a hydrocarbon-based polymer that imparts excellent oil resistance and, if desired, excellent water resistance to paper. The hydrocarbon-based polymer comprises repeating units formed by monomers having a hydrocarbon group having 1 to 40 carbon atoms and an NH-containing group, in an amount of 80% by weight or more relative to the polymer. Preferably, the hydrocarbon-based polymer comprises: (a) repeating units formed by acrylic monomers having a hydrocarbon group having 1 to 40 carbon atoms and an NH-containing group, and (b) repeating units formed by acrylic monomers having a hydrophilic group.

Description

Technical Field

[0001] The present disclosure relates to an oil-resistant agent composition and paper treated with the oil-resistant agent composition. Prior Art

[0002] For food packaging materials and food containers made of paper, it is required to prevent the leakage of moisture and oil from food. Therefore, oil-resistant agents are applied to be added internally or externally to paper.

[0003] Patent Document 1 (Japanese Patent Publication No. WO2020 / 054856) discloses an oil-resistant agent for paper containing a non-fluorinated copolymer having: (a) a repeating unit formed from an acrylic monomer having a long-chain hydrocarbon group with 7 to 40 carbon atoms, and (b) a repeating unit formed from an acrylic monomer having a hydrophilic group. Patent Document 2 (Japanese Patent Publication No. WO2020 / 241709) discloses the content of imparting high-temperature oil resistance performance by a non-fluorinated polymer and inorganic particles or organic particles. Patent Document 3 (Japanese Unexamined Patent Application Publication No. 2018-16902) discloses a water-repellent agent for paper containing: a polymer containing a vinyl monomer having a long-chain alkyl group with 14 or more carbon atoms as a polymerization component. [Prior Art Documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. WO2020 / 054856 [Patent Document 2] Japanese Patent Publication No. WO2020 / 241709 [Patent Document 3] Japanese Unexamined Patent Application Publication No. 2018-16902 Summary of the Invention Problems to be Solved by the Invention

[0005] An object of the present disclosure is to provide an oil-resistant agent composition (oil-resistant agent) that can impart excellent oil resistance and, if necessary, excellent water resistance to paper. Means for Solving the Problems

[0006] The oil-resistant agent composition of the present disclosure contains a hydrocarbon group-containing polymer (i.e., a non-fluorinated polymer). The hydrocarbon group-containing polymer preferably has a repeating unit formed from a monomer having a hydrocarbon group with 1 to 40 carbon atoms and a group containing an NH group in an amount of 80% by weight or more relative to the polymer. In hydrocarbon-containing polymers, it is preferable that there is an NH-containing group between the polymer backbone and the hydrocarbon group having 1 to 40 carbon atoms. The hydrocarbon-containing polymers are preferably polyolefins, polyacrylic acid, polyesters, polyamides, polycarbonates, or polyurethane.

[0007] Hydrocarbon-containing polymers preferably have a softening point above 65°C. The softening point of hydrocarbon-containing polymers can be above 65℃, 66℃, 68℃, 70℃, 72℃, 74℃, 76℃, 78℃, 80℃, 82℃, 84℃, 86℃, 88℃, 90℃, 92℃, 94℃, 96℃, 98℃, or 100℃. The upper limit of the softening point of hydrocarbon-containing polymers can be 210℃, 200℃, 190℃, 180℃, 150℃, 140℃, 130℃, 120℃, or 110℃. The term "softening point" refers to the temperature at which the complex viscosity of a polymer is 1.0 × 10⁴, as determined by dynamic mechanical analysis (DMA).

[0008] Hydrocarbon-containing polymers are polymers having hydrocarbon groups having 1 to 40 carbon atoms, especially 3 to 40 or 7 to 40.

[0009] The preferred embodiment of the invention is described below. Pattern 1: An oil-resistant agent composition contains a hydrocarbon-containing polymer, wherein the hydrocarbon-containing polymer comprises repeating units formed by monomers having hydrocarbon groups having 1 to 40 carbon atoms and NH groups in an amount of 80% by weight or more relative to the polymer. Pattern 2: The oil-resistant agent composition as described in Sample 1, wherein the hydrocarbon-containing polymer is a polyolefin, polyacrylic acid, polyester, polyamide, polycarbonate or polyurethane with an NH-containing group between the polymer backbone and the hydrocarbon group. Pattern 3: The oil-resistant agent composition as described in Sample 1 or 2, wherein the hydrocarbon-containing polymer has repeating units formed by vinyl carbon-carbon double bonds of monomers having NH groups between the polymer backbone and the hydrocarbon groups. Pattern 4: The oil-resistant agent composition as described in any one of samples 1 to 3, wherein the hydrocarbon-containing polymer has: (a) Repeating units formed from acrylic acid monomers having hydrocarbon groups having 1 to 40 carbon atoms and NH-containing groups, and (b) Repeating units formed from acrylic monomers having hydrophilic groups. Pattern 5: The oil-resistant agent composition as described in Sample 4, wherein the hydrocarbon-containing polymer further has: Repeating units other than monomers (a) and (b) formed by monomers (c) having ethylene carbon-carbon double bonds and anionic or cationic donor groups. Pattern 6: The oil-resistant composition as described in any one of samples 1 to 5, wherein the softening point of the hydrocarbon-containing polymer is above 80°C. Pattern 7: Oil-resistant compositions as described in any one of samples 1 to 6, wherein the hydrocarbon-containing polymer is obtained by emulsification polymerization. Pattern 8: The oil-resistant agent composition described in any one of samples 1 to 7 further contains at least one emulsifier selected from cationic emulsifiers, nonionic emulsifiers and anionic emulsifiers. Pattern 9: The oil-resistant composition as described in any one of Examples 5 to 8, wherein the amount of repeating units formed by acrylic monomers (a) having hydrocarbon groups is 80 to 99% by weight relative to the polymer, the amount of repeating units formed by acrylic monomers (b) having hydrophilic groups is 1 to 15% by weight relative to the polymer, and the amount of repeating units formed by monomers (c) having anionic or cationic donor groups is 0 to 20% by weight relative to the polymer. Pattern 10: The oil-resistant agent composition described in any one of samples 1 to 9 further contains water or a liquid medium that is a mixture of water and an organic solvent. Pattern 11: An oil-resistant paper having a hydrocarbon-containing polymer in an oil-resistant agent composition as described in any one of examples 1 to 10 attached to the paper. Pattern 12: The oil-resistant paper described in specimen 11 is a pulp molded product. Pattern 13: Oil-resistant paper as described in specimen 11 or 12 is food packaging material or food container. Pattern 14: A method for manufacturing paper involves treating the paper with an oil-resistant agent composition as described in any one of embodiments 1 to 10 by means of external or internal treatment. Pattern 15: The method for manufacturing paper as described in Mode 14, wherein the conductivity of the pulp slurry is 0.1 to 2000 μS / cm, the pH of the pulp slurry is 4 to 9, and the hardness of the water used in the pulp slurry is 5000 ppm or less. Mode 16: A method for manufacturing a pulp mold, comprising: filling the oil-resistant agent composition and the pulp slurry as described in any one of Modes 1 to 10 into a mold, and allowing water to pass through outside the mold to form a pulp. Effect of the invention

[0010] According to the present disclosure, excellent oil resistance and water resistance are imparted to the paper. The paper has excellent oil resistance and water resistance even at high temperatures of 60°C to 110°C, for example, 65°C to 100°C. Embodiment

[0011] The hydrocarbon group-containing polymer has a hydrocarbon group with 1 to 40 carbon atoms and is a polyolefin, polyacrylic acid, polyester, polyamide, polycarbonate, or polyurethane. The hydrocarbon group-containing polymer is preferably a polymer polymerized from ethylenic carbon-carbon double bonds. The hydrocarbon group-containing polymer preferably has repeating units derived from monomers having a hydrocarbon group with 1 to 40 carbon atoms. Preferably, there is a group containing an NH group between the polymer main chain and the hydrocarbon group.

[0012] The monomer having a hydrocarbon group with 1 to 40 carbon atoms is not limited, preferably a monomer having an ethylenic carbon-carbon double bond, and particularly preferably an acrylic monomer. In the monomer having a hydrocarbon group with 1 to 40 carbon atoms, preferably, there is a group containing an NH group between the hydrocarbon group with 1 to 40 carbon atoms and the ethylenic carbon-carbon double bond. Examples of the group containing an NH group are an amide group, an urethane group, a urea group, and a sulfonamide group.

[0013] The preferred hydrocarbon group-containing polymer has: (a) Repeating units formed from an acrylic monomer having a hydrocarbon group with 1 to 40 carbon atoms and a group containing an NH group, and (b) Repeating units formed from an acrylic monomer having a hydrophilic group.

[0014] Furthermore, in addition to monomers (a) and (b), the hydrocarbon group-containing polymer preferably has: repeating units formed from (c) a monomer having an ion-donating group. In addition to monomers (a), (b), and (c), the hydrocarbon group-containing polymer may also have: repeating units formed from (d) other monomers.

[0015] (a) Acrylic monomers with hydrocarbon groups The acrylic monomer (a) having a hydrocarbon group has a hydrocarbon group having 1 to 40, 3 to 40, or 7 to 40 carbon atoms. The hydrocarbon group having 1 to 40 carbon atoms is preferably a straight-chain or branched hydrocarbon group having 1 to 40 carbon atoms. Because high oil resistance can be obtained, the hydrocarbon group preferably has 10 to 40 carbon atoms, for example, 12 to 30, and particularly preferably 15 to 30. Alternatively, the hydrocarbon group may have 18 to 40 carbon atoms.

[0016] The acrylic monomer (a) having a hydrocarbon group is preferably a compound represented by the following formula (acrylate monomer or acrylamide monomer): CH2=C(-X1)-C(=O)-Y1-Z(-Y2-R1)n In the formula, R1 is independently a hydrocarbon group having 1 to 40 carbon atoms. X1 is a hydrogen atom, a monovalent organic group, or a halogen atom. Y1 is either -O- or -NH-. Y2 is a group containing an NH group. Z is a directly bonded hydrocarbon group, or a divalent or trivalent hydrocarbon group with 1 to 5 carbon atoms. n is 1 or 2.

[0017] X1 can be a hydrogen atom, a methyl group, a halogen excluding a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. Examples of X1 are hydrogen atoms, methyl groups, chlorine atoms, bromine atoms, iodine atoms, and cyano groups. X1 is preferably a hydrogen atom, a methyl group, or a chlorine atom. X1 is particularly preferably a hydrogen atom.

[0018] Y1 is either -O- or -NH-, with -O- being preferred.

[0019] Z is a direct bond, or a alkyl group with 1 to 5 carbon atoms in a divalent or trivalent state. Z can have a straight-chain structure or a branched structure. The number of carbon atoms in Z is preferably 2 to 4, and particularly preferably 2. Specific examples of Z include: direct bond, -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH2CH= with a branched structure, -CH2(CH-)CH2- with a branched structure, -CH2CH2CH= with a branched structure, -CH2CH2CH2CH2CH= with a branched structure, -CH2CH2(CH-)CH2- with a branched structure, and -CH2CH2CH2CH= with a branched structure. Z is preferably a alkyl group with 1 to 5 carbon atoms in a divalent state.

[0020] Y2 is a spacer group containing an NH group. Y2 forms spacer sites in the polymer that can form hydrogen bonds. This can be considered as improving oil resistance in the polymer by forming hydrogen bonds through the NH group. Y2 is preferably amide, ethyl carbamate, urea, or sulfonamide. That is, the NH-containing group is preferably -NH-C(=O)-, -C(=O)-NH-, -OC(=O)-NH-, -NH-C(=O)-O-, or -NH-C(=O)-NH-, -NH-S(=O)2-, or -S(=O)2-NH-.

[0021] n can be 1 or 2, with 1 being preferable.

[0022] A preferred example of an acrylic monomer (a) that is an acrylate monomer and has a divalent Z-group is: CH2=C(-X1)-C(=O)-O-(CH2)m-NH-C(=O)-R1, CH2=C(-X1)-C(=O)-O-(CH2)mC(=O)-NH-R1, CH2=C(-X1)-C(=O)-O-(CH2)mOC(=O)-NH-R1, CH2=C(-X1)-C(=O)-O-(CH2)m-NH-C(=O)-O-R1, CH2=C(-X1)-C(=O)-O-(CH2)m-NH-C(=O)-NH-R1, CH2=C(-X1)-C(=O)-O-(CH2)m-NH-S(=O)2-R1, CH2=C(-X1)-C(=O)-O-(CH2)mS(=O)2-NH-R1. The preferred form is CH2=C(-X1)-C(=O)-O-(CH2)m-NH-C(=O)-R1. In the above formula, X1 and R1 have the same meaning as above, and m is 1 to 5.

[0023] A preferred example of an acrylic monomer (a) that is an acrylate monomer and has a trivalent Z-group is:

[0024] Acrylic acid monomer (a) can be produced by reacting hydroxyalkyl (meth)acrylate or hydroxyalkyl (meth)acrylamide with alkyl isocyanate. Examples of alkyl isocyanates include lauryl isocyanate, myristyl isocyanate, cetyl isocyanate, stearyl isocyanate, oleyl isocyanate, and docosyl isocyanate. Alternatively, acrylic monomer (a) can also be reacted with (meth)acrylates having isocyanate groups on the side chain, such as 2-methacryloxyethyl isocyanate, to produce an alkylamine or alkanol. Examples of alkylamines include laurylamine, myristicamine, cetylamine, stearylamine, oleylamine, and docosylamine. Examples of alkanols include lauryl alcohol, myristic alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and docosyl alcohol.

[0025] The preferred acrylic monomer (a) with a hydrocarbon group is an acrylate in which X1 is a hydrogen atom.

[0026] The acrylic monomer (a) is preferably a amide-containing monomer represented by the following formula: R12-C(=O)-NH-R13-O-R11 In the formula, R11 is an organic residual group with ethylene-like unsaturated polymerizable groups. R12 is a hydrocarbon group with 1 to 40 carbon atoms. R13 is a hydrocarbon group with 1 to 5 carbon atoms.

[0027] R11 is an organic residual group with an ethylene-unsaturated polymerizable group, and is not particularly limited as long as it has a double bond between carbon atoms. Specifically, examples include: -C(=O)CR14=CH2, -CHR14=CH2, -CH2CHR14=CH2, etc., which are organic residual groups with an ethylene-unsaturated polymerizable group. R14 can include hydrogen atoms or alkyl groups with 1 to 4 carbon atoms. In addition to ethylene-unsaturated polymerizable groups, R11 can also have various organic groups, such as: chain hydrocarbons, cyclic hydrocarbons, polyoxyalkylene groups, polysiloxane groups, etc., which can be substituted by various substituents. R11 is preferably -C(=O)CR14=CH2.

[0028] R12 is a hydrocarbon group having 1 to 40 carbon atoms, preferably an alkyl group, and may include chain hydrocarbon groups, cyclic hydrocarbon groups, etc. Among them, chain hydrocarbon groups are preferred, and straight-chain saturated hydrocarbon groups are particularly preferred. The number of carbon atoms in R12 is 1 to 40, preferably 11 to 27, and particularly preferably 15 to 23.

[0029] R13 is a hydrocarbon group having 1 to 5 carbon atoms, preferably an alkyl group. The hydrocarbon group having 1 to 5 carbon atoms can be either straight-chain or branched-chain, and can have unsaturated bonds, but is preferably straight-chain. R13 preferably has 2 to 4 carbon atoms, and more preferably 2. R13 is preferably an alkyl group.

[0030] The amino-containing monomer can be one with one type of R12 (e.g., a compound with only R12 having 17 carbons) or a combination of multiple types of R12 (e.g., a mixture of a compound with R12 having 17 carbons and a compound with R12 having 15 carbons).

[0031] An example of a monomer containing a amide group is carboxyamide alkyl (meth)acrylate. Specific examples of monomers containing acetyl groups include: ethyl palmitate (meth)acrylate, ethyl stearate (meth)acrylate, ethyl creosinate (meth)acrylate, ethyl myristate (meth)acrylate, ethyl lauryl (meth)acrylate, ethyl isostearate (meth)acrylate, ethyl oleate (meth)acrylate, ethyl tributylcyclohexylhexyl (meth)acrylate, ethyl adamantane carboxylate (meth)acrylate, ethyl naphthyl carboxylate (meth)acrylate, ethyl anthracene carboxylate (meth)acrylate, propyl palmitate (meth)acrylate, propyl stearate (meth)acrylate, ethyl palmitate vinyl ether, ethyl stearate vinyl ether, ethyl palmitate allyl ether, ethyl stearate allyl ether, or mixtures thereof.

[0032] The acetylamino monomer is preferably stearylaminoethyl (meth)acrylate. The acetylamino monomer may be a mixture containing stearylaminoethyl (meth)acrylate. In the mixture containing stearylaminoethyl (meth)acrylate, the amount of stearylaminoethyl (meth)acrylate relative to the total weight of the acetylamino monomer is, for example, 55 to 99% by weight, preferably 60 to 85% by weight, more preferably 65 to 80% by weight, and the remaining monomer may be, for example, palmitylaminoethyl (meth)acrylate.

[0033] (b) Acrylic monomers with hydrophilic groups The acrylic monomer (b) having a hydrophilic group is a monomer other than monomer (a), and is a hydrophilic monomer. The hydrophilic group is preferably an oxoalkyl group (the alkyl group has 2 to 6 carbon atoms). In particular, the acrylic monomer (b) having a hydrophilic group is preferably polyalkylene glycol mono(meth)acrylate and / or polyalkylene glycol di(meth)acrylate, polyalkylene glycol mono(meth)acrylamide. Polyalkylene glycol mono(meth)acrylate and polyalkylene glycol di(meth)acrylate, polyalkylene glycol mono(meth)acrylamide, are preferably represented by the following general formula: CH2=CX2C(=O)-O-(RO)n-X3 (b1) CH2=CX2C(=O)-O-(RO)nC(=O)CX2=CH2 (b2), or CH2=CX2C(=O)-NH-(RO)n-X3 (b3) In the formula, X2 can be a hydrogen atom or a methyl group independently. X3 can be independently a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms. R is an alkyl group having 2 to 6 carbon atoms. n is an integer from 1 to 90. n can be, for example, 1 to 50, especially 1 to 30, and particularly 1 to 15 or 2 to 15. Alternatively, n can be, for example, 1. R can be a straight-chain or branched alkyl group, for example, a group represented by the formula -(CH2)x- or -(CH2)x1-(CH(CH3))x2- [where x1 and x2 are 0 to 6, for example 2 to 5, and the sum of x1 and x2 is 1 to 6; the order of -(CH2)x1- and -(CH(CH3))x2- is not limited to the formula described, and can be random]. In -(RO)n-, R is two or more (e.g., two to four, especially two), and -(RO)n- can be, for example, a combination of -(R1O)n1- and -(R2O)n2- [where R1 and R2 are different from each other, being alkyl groups with 2 to 6 carbon atoms, n1 and n2 are 1 or more, and the sum of n1 and n2 is 2 to 90].

[0034] In general formulas (b1), (b2), and (b3), R is preferably ethyl, propyl, or butyl. R in general formulas (b1), (b2), and (b3) can be a combination of two or more alkyl groups. In this case, it is preferable that at least one R is ethyl, propyl, or butyl. Examples of R combinations include: ethyl / propyl combinations, ethyl / butyl combinations, and propyl / butyl combinations. Monomer (b) can be a mixture of two or more. In this case, at least one of the monomers (b) is preferably an ethyl, propyl, or butyl group from general formula (b1) or (b2), (b3). Furthermore, when using polyalkylene glycol di(meth)acrylate represented by general formula (b2), it is not desirable to use it alone as monomer (b); it is preferable to use it in combination with monomer (b1). In this case, the compound represented by general formula (b2) preferably does not exceed 30% by weight in the monomer (b) used.

[0035] Specific examples of acrylic monomers (b) having hydrophilic groups are shown below, but are not limited to these. CH2=CHCOO-CH2CH2O-H CH2=CHCOO-CH2CH2CH2O-H CH2=CHCOO-CH2CH(CH3)OH CH2=CHCOO-CH(CH3)CH2O-H CH2=CHCOO-CH2CH2CH2CH2O-H CH2=CHCOO-CH2CH2CH(CH3)OH CH2=CHCOO-CH2CH(CH3)CH2O-H CH2=CHCOO-CH(CH3)CH2CH2O-H CH2=CHCOO-CH2CH(CH2CH3)OH CH2=CHCOO-CH2C(CH3)2O-H CH2=CHCOO-CH(CH2CH3)CH2O-H CH2=CHCOO-C(CH3)2CH2O-H CH2=CHCOO-CH(CH3)CH(CH3)OH CH2=CHCOO-C(CH3)(CH2CH3)OH 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)9O-CH3

[0036] 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

[0037] CH2=CHCOO-(CH2CH2O)9-H CH2=C(CH3)COO-CH2CH2O-H CH2=C(CH3)COO-CH2CH2CH2O-H CH2=C(CH3)COO-CH2CH(CH3)OH CH2=C(CH3)COO-CH(CH3)CH2O-H CH2=C(CH3)COO-CH2CH2CH2CH2O-H CH2=C(CH3)COO-CH2CH2CH(CH3)OH CH2=C(CH3)COO-CH2CH(CH3)CH2O-H CH2=C(CH3)COO-CH(CH3)CH2CH2O-H CH2=C(CH3)COO-CH2CH(CH2CH3)OH 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)OH CH2=C(CH3)COO-C(CH3)(CH2CH3)OH 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

[0038] 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

[0039] CH2=CH-C(=O)-NH-CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH(CH3)O-H CH2=CH-C(=O)-NH-CH(CH3)CH2O-H CH2=CH-C(=O)-NH-CH2CH2CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH2CH(CH3)OH CH2=CH-C(=O)-NH-CH2CH(CH3)CH2O-H CH2=CH-C(=O)-NH-CH(CH3)CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH(CH2CH3)OH 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

[0040] 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

[0041] 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-CH2CH2CH(CH3)OH CH2=C(CH3)-C(=O)-NH-CH2CH(CH3)CH2O-H CH2=C(CH3)-C(=O)-NH-CH(CH3)CH2CH2O-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

[0042] 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

[0043] Monomer (b) is preferably an acrylate or acrylamide in which X2 is a hydrogen atom. It is particularly preferably hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate or hydroxyethyl acrylamide.

[0044] (c) Monomers having ion donor bases The monomer (c) having an ion donor group is a monomer other than monomers (a) and (b). Monomer (c) is preferably a monomer having an vinyl carbon-carbon double bond and an ion donor group. The ion donor group is an anion donor group and / or a cation donor group.

[0045] Monomers with an anionic donor group can be listed as monomers having a carboxyl group, a sulfonic acid group, or a phosphate group. Specific examples of monomers with an anionic donor group are: (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, vinyl sulfonic acid, (meth)allyl sulfonic acid, styrene sulfonic acid, meth phosphate, vinylbenzene sulfonic acid, acrylamide tributyl sulfonic acid, etc., or their salts.

[0046] Salts that can be anionic donors include: alkali metal salts, alkaline earth metal salts, or ammonium salts, such as methylammonium salts, ethanolammonium salts, triethanolammonium salts, etc.

[0047] In monomers having a cationic donor group, examples of the cationic donor group are amino groups, preferably tertiary and quaternary amino groups. In the tertiary amino group, the two groups bonded to the nitrogen atom are preferably the same or different aliphatic groups (especially alkyl) having 1 to 5 carbon atoms, aromatic groups (aryl) having 6 to 20 carbon atoms, or aromatic aliphatic groups (especially aralkyl, e.g., benzyl (C6H5-CH2-)) having 7 to 25 carbon atoms. In the quaternary amino group, the three groups bonded to the nitrogen atom are preferably the same or different aliphatic groups (especially alkyl) having 1 to 5 carbon atoms, aromatic groups (aryl) having 6 to 20 carbon atoms, or aromatic aliphatic groups (especially aralkyl, e.g., benzyl (C6H5-CH2-)) having 7 to 25 carbon atoms. In both the tertiary and quaternary amino groups, the remaining group bonded to the nitrogen atom may have a carbon-carbon double bond. The cationic donor group may also be in the form of a salt.

[0048] The cation donor group of the salt is a salt of an acid (organic or inorganic). Organic acids are preferred, such as carboxylic acids having 1 to 20 carbon atoms (especially monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and stearic acid). Dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate and their salts are preferred.

[0049] Specific examples of monomers having cationic donor groups are shown below. CH2=CHCOO-CH2CH2-N(CH3)2 and its salts (e.g., acetates) CH2=CHCOO-CH2CH2-N(CH2CH3)2 and its salts (e.g., acetates) CH2=C(CH3)COO-CH2CH2-N(CH3)2 and its salts (e.g., acetates) CH2=C(CH3)COO-CH2CH2-N(CH2CH3)2 and its salts (e.g., acetates) CH2=CHC(O)N(H)-CH2CH2CH2-N(CH3)2 and its salts (e.g., acetates) CH2=CHCOO-CH2CH2-N(-CH3)(-CH2-C6H5) and its salts (e.g., acetates) CH2=C(CH3)COO-CH2CH2-N(-CH2CH3)(-CH2-C6H5) and their salts (e.g., acetates) 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-

[0050] The monomer (c) having an ion-donating group is preferably methacrylic acid, acrylic acid and dimethylaminoethyl methacrylate, more preferably methacrylic acid and dimethylaminoethyl methacrylate.

[0051] (d) Other monomers Other monomers (d) are monomers other than monomers (a), (b), and (c). Examples of other monomers include: ethylene, vinyl acetate, vinyl chloride, vinyl fluoride, halogenated vinyl styrene, α-methylstyrene, p-methylstyrene, polyoxyalkylene mono(meth)acrylate, (meth)acrylamide, diacetone (meth)acrylamide, hydroxymethylated (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, alkyl vinyl ethers, halogenated alkyl vinyl ethers, alkyl vinyl ketones, butadiene, isoprene, chloroprene, glycidyl (meth)acrylate, aziridinium (meth)acrylate, benzyl (meth)acrylate, ethyl (meth)acrylate isocyanate, cyclohexyl (meth)acrylate, isoborneol (meth)acrylate, short-chain alkyl (meth)acrylates, maleic anhydride, (meth)acrylates containing polydimethylsiloxane, and N-vinyl carbazole.

[0052] The amount of repeating unit (repeating unit (a)) formed by monomer (a) relative to the hydrocarbon-containing polymer (or relative to the sum of repeating unit (a) and repeating unit (b)) may be 80% by weight or more, 82% by weight or more, 84% by weight or more, 86% by weight or more, 88% by weight or more, 90% by weight or more, 91% by weight or more, 92% by weight or more, 93% by weight or more, 94% by weight or more, or 95% by weight or more. The amount of repeating unit (repeating unit (a)) formed by monomer (a) relative to the hydrocarbon-containing polymer (or relative to the sum of repeating unit (a) and repeating unit (b)) may be 99% by weight or less, 98% by weight or less, 96% by weight or less, 95% by weight or less, 94% by weight or less, 92% by weight or less, or 90% by weight or less.

[0053] The amount of repeating unit (repeating unit (b)) formed by monomer (b) relative to the hydrocarbon-containing polymer (or relative to the sum of repeating unit (a) and repeating unit (b)) may be 0.5 to 15 wt%, 1 to 13 wt%, 3 to 12 wt%, 4 to 11 wt%, 5 to 10 wt%, 6 to 9 wt%, or 7 to 8 wt%. The amount of repeating units formed by monomer (c) relative to the hydrocarbon-containing polymer can be 0 to 15 wt%, 0.3 to 10 wt%, 0.5 to 8 wt%, 0.8 to 7 wt%, 1 to 6 wt%, 1.5 to 5 wt%, 1.8 to 4 wt%, or 2 to 3 wt%. The amount of repeating units formed by monomer (d) relative to the hydrocarbon-containing polymer can be 1 to 10 wt%, 2 to 9 wt%, 3 to 8 wt%, 4 to 7 wt%, or 5 to 6 wt%.

[0054] The weight-average molecular weight of the hydrocarbon-containing polymer can be from 1,000 to 10,000,000 or 100,000,000, more preferably from 5,000 to 8,000,000 or 80,000,000, and even more preferably from 10,000 to 4,000,000 or 40,000,000. The weight-average molecular weight is a value obtained by gel permeation chromatography and converted to polystyrene. In this specification, "(meth)acrylic acid" means acrylic acid or methacrylic acid. For example, "(meth)acrylate" means acrylate or methacrylate.

[0055] From the perspective of oil resistance, hydrocarbon-containing polymers are better than random copolymers compared to block copolymers.

[0056] There are no particular limitations on the polymerization of hydrocarbon-containing polymers; various polymerization methods can be selected, such as bulk polymerization, solution polymerization, emulsion polymerization, and radiation polymerization. For example, solution polymerization using organic solvents or emulsion polymerization using water or organic solvents and water can generally be chosen. After polymerization, the solution is diluted with water and emulsified in water to prepare a treatment solution. In this disclosure, after polymerization (e.g., solution polymerization or emulsion polymerization, preferably solution polymerization), desolvation is preferably performed after the addition of water to disperse the polymer in water. This allows for the manufacture of self-dispersible articles without the need for the addition of emulsifiers. In this disclosure, emulsion polymerization is preferred. Compared to solution polymerization, emulsion polymerization imparts polymers with superior high-temperature oil resistance for the same monomer composition.

[0057] Organic solvents can be listed as follows: ketones such as acetone and butanone; esters such as ethyl acetate and methyl acetate; diols such as propylene glycol, dipropylene glycol monomethyl ether, N-methyl-2-pyrrolidone (NMP), dipropylene glycol, tripropylene glycol, and low molecular weight polyethylene glycol; and alcohols such as ethanol and isopropanol.

[0058] Polymerization initiators can be, for example, peroxides, azo compounds, or persulfate-based compounds. Generally, polymerization initiators are water-soluble and / or oil-soluble. Specific examples of oil-soluble polymerization initiators include: 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylpentanitrile), 2,2'-azobis(2,4-dimethyl-4-methoxypentanitrile), 1,1'-azobis(cyclohexane-1-carboxynitrile), dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-isobutyronitrile), benzyl peroxide, di(tert-butyl peroxide), lauryl peroxide, cumene hydroperoxide, tributyl peroxytrimethylacetate, diisopropyl peroxydicarbonate, tributyl peroxytrimethylacetate, etc.

[0059] In addition, preferred examples of water-soluble polymerization initiators include: 2,2'-azobisisobutylamidine dihydrochloride, 2,2'-azobis(2-methylpropanediamine) dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] hydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] sulfate hydrate, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane] hydrochloride, potassium persulfate, barium persulfate, ammonium persulfate, hydrogen peroxide, etc. The polymerization initiator is used in the range of 0.01 to 5 parts by weight relative to 100 parts by weight of monomer.

[0060] Furthermore, for the purpose of molecular weight adjustment, chain transfer agents can be used, such as thiol-containing compounds, including 2-mercaptoethanol, mercaptopropionic acid, and alkyl thiols. The thiol-containing compound is used in amounts of 10 parts by weight or less relative to 100 parts by weight of the monomer, for example, in the range of 0.01 to 5 parts by weight.

[0061] Specifically, hydrocarbon-containing polymers can be manufactured in the following ways. In solution polymerization, the method involves dissolving the monomer in an organic solvent, substituting it with nitrogen, adding a polymerization initiator, and then heating and stirring at a temperature of 40 to 120°C for 1 to 10 hours. The polymerization initiator is generally an oil-soluble polymerization initiator.

[0062] Organic solvents that are inert to monomers and can dissolve them include: ketones such as acetone and butanone; esters such as ethyl acetate and methyl acetate; glycols such as propylene glycol, dipropylene glycol monomethyl ether, N-methyl-2-pyrrolidone (NMP), dipropylene glycol, tripropylene glycol, and low molecular weight polyethylene glycol; alcohols such as ethanol and isopropanol; and hydrocarbon solvents such as n-heptane, n-hexane, n-octane, cyclohexane, methylcyclohexane, cyclopentane, methylcyclopentane, methylpentane, 2-ethylpentane, isoparaffinic hydrocarbons, flowing paraffin, decane, undecane, dodecane, mineral oil, pine resin, and naphtha. Preferred examples of solvents include: acetone, chloroform, HCHC225, isopropanol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, butanone, methyl isobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, N-methyl-2-pyrrolidone (NMP), dipropylene glycol monomethyl ether (DPM), etc. The total amount of organic solvent relative to the monomer is in the range of 50 to 2000 parts by weight, for example, 50 to 1000 parts by weight.

[0063] In emulsion polymerization, the method involves emulsifying the monomer in water in the presence of an emulsifier, followed by nitrogen substitution, adding a polymerization initiator, and stirring at 40 to 80°C for 1 to 10 hours to carry out polymerization. The polymerization initiator used is a water-soluble polymerization initiator, such as 2,2'-azobisisobutylamidine dihydrochloride, 2,2'-azobis(2-methylpropanediamine) hydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] hydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] sulfate hydrate, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane] hydrochloride, potassium persulfate, barium persulfate, ammonium persulfate, hydrogen peroxide; and... Oil-soluble polymerization initiators, such as 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylpentanitrile), 2,2'-azobis(2,4-dimethyl4-methoxypentanitrile), 1,1'-azobis(cyclohexane-1-carboxynitrile), dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-isobutyronitrile), benzyl peroxide, di(tert-butyl peroxide), lauryl peroxide, cumene hydroperoxide, tributyl peroxytrimethylacetate, diisopropyl peroxydicarbonate, tributyl peroxytrimethylacetate, etc. The polymerization initiator is used in the range of 0.01 to 10 parts by weight relative to 100 parts by weight of monomer.

[0064] To obtain a polymer aqueous dispersion with excellent storage stability, it is preferable to use an emulsification device, such as a high-pressure homogenizer or an ultrasonic homogenizer, which can impart strong crushing energy, to micronize the monomers in water, and then use an oil-soluble polymerization initiator for polymerization. Furthermore, various anionic, cationic, or nonionic emulsifiers can be used, in the range of 0.5 to 20 parts by weight relative to 100 parts by weight of monomers. Anionic and / or nonionic and / or cationic emulsifiers are preferred. When the monomers are not completely compatible, it is preferable to add a compatibilizer to ensure sufficient compatibility, such as a water-soluble organic solvent or a low molecular weight monomer. The addition of a compatibilizer can improve emulsification and copolymerization properties.

[0065] Water-soluble organic solvents include acetone, propylene glycol, dipropylene glycol monomethyl ether (DPM), dipropylene glycol, tripropylene glycol, ethanol, N-methyl-2-pyrrolidone (NMP), 3-methoxy-3-methyl-1-butanol, or isopentyl glycol, etc., which can be used in the range of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, relative to 100 parts by weight of water. The stability of the composition (especially the emulsion) is improved by adding NMP, DPM, 3-methoxy-3-methyl-1-butanol, or isopentyl glycol (preferably in an amount of, for example, 1 to 20% by weight, especially 3 to 10% by weight, relative to the composition). Furthermore, low molecular weight monomers include methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, etc., which can be used in the range of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, relative to 100 parts by weight of the total monomer.

[0066] The oil-resistant agent composition is preferably in the form of a solution, emulsion, or aerosol. The oil-resistant agent composition contains a hydrocarbon-based polymer and a medium (e.g., an organic solvent and a liquid medium such as water). The oil-resistant agent composition is preferably an aqueous dispersion of a hydrocarbon-based polymer. In the oil-resistant agent composition, the concentration of the hydrocarbon-containing polymer can be, for example, from 0.01 to 50 by weight.

[0067] The ionic charge density of the oil-resistant agent composition can be above -5000 μeq / g, above -2500 μeq / g, above -1500 μeq / g, above -500 μeq / g, above 0 μeq / g, above 100 μeq / g, or above 200 μeq / g, preferably above -2500 μeq / g, more preferably above -400 μeq / g, for example, above 0 μeq / g. The ionic charge density of the oil-resistant agent composition can be below 7500 μeq / g, below 5000 μeq / g, below 2500 μeq / g, below 1000 μeq / g, below 500 μeq / g, below 350 μeq / g, below 300 μeq / g, or below 250 μeq / g, preferably below 5000 μeq / g, more preferably below 800 μeq / g, for example, below 300 μeq / g. In particular, the ionic charge density of the oil-resistant agent composition is preferably -2500 to 5000 μeq / g, more preferably -400 to 800 μeq / g (e.g., 210 μeq / g, 250 μeq / g, or 300 μeq / g). The ionic charge density of the oil-resistant agent composition can be determined, for example, by the following methods. <Determination of Ion Charge Density> Using a 1 / 1000 equivalent potassium polyvinyl sulfonate solution, the anion requirement of a 0.1 g / L sample aqueous solution was determined using a particle charge analyzer (BTG MUTEK PCD-04), and the ionic charge density (cation charge density) was calculated from the following formula (1). Alternatively, a polyallyldimethylammonium chloride solution was used instead of potassium polyvinyl sulfonate, and the cation requirement was similarly determined, and the ionic charge density (anion charge density) was calculated from the following formula (1). [Number 1] Ion charge density (μeq / g) = A / B (1) A: Cation requirement or anion requirement (μeq / L) B: Sample solution concentration (g / L)

[0068] The removal of organic solvents from polymer solutions can be achieved by heating the polymer solution (preferably under reduced pressure) (e.g., above 30°C, e.g., 50 to 120°C).

[0069] Oil-resistant agents can be used to treat paper substrates (e.g., surface treatment, internal treatment). Oil-resistant agents can be applied to the workpiece using known methods. Typically, this involves dispersing the oil-resistant agent in an organic solvent or water for dilution, then adhering it to the surface of the workpiece using known methods such as dip coating, spray coating, or bubble coating, followed by drying (surface treatment). Alternatively, the oil-resistant agent can be added to pulp slurry and then dehydrated, formed, and dried using known methods (internal treatment). Examples of paper substrates that can be processed include: paper, containers made of paper, and molded objects made of paper (such as pulp molds). The hydrocarbon-containing polymer system disclosed herein adheres well to paper substrates.

[0070] Paper can be manufactured using conventional papermaking methods. Methods include: internal treatment by adding an oil-resistant agent composition to the pulp before papermaking, or external treatment by applying the oil-resistant agent composition to the paper after papermaking. The method of treating the oil-resistant agent composition disclosed herein is preferably an internal treatment method.

[0071] The application of adhesives in additional treatment methods can also be distinguished by the different coating methods, as follows. One coating method involves supplying the coating liquid (sizing liquid) to a pressing section formed between two rubber rollers to create a coating liquid reservoir, called a pool. The paper is then passed through this reservoir to coat both sides with the sizing liquid, a process known as pool-type two-roll sizing. Other coating methods include guillotine roll sizing using a surface transfer die and rod metering size press sizing. In pool-type two-roll sizing, the sizing liquid easily penetrates into the paper, while in surface transfer sizing, the sizing liquid components tend to remain on the paper surface. Compared to pool-type two-roll sizing, surface transfer sizing results in a coating layer that remains more firmly on the paper surface, forming a more robust oil-resistant layer. In this disclosure, even when using the former type of pool-type two-roll sizing, oil resistance can be imparted to the paper. After simple drying at room temperature or high temperature, the paper treated in this way is subjected to heat treatment at temperatures ranging from 200°C to 300°C, depending on the properties of the paper, in particular from 80°C to 180°C, thereby exhibiting excellent oil and water resistance.

[0072] This disclosure applies to: gypsum board base paper, coated base paper, medium-strength paper, general lining and corrugated core paper, neutral pure white roll paper, neutral lining, rust-proof lining and metal composite paper, kraft paper, etc. Furthermore, it can also be used in: neutral printing and note-taking paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper, and neutral information paper.

[0073] The pulp raw materials can be any of the following: bleached or unbleached chemical pulps such as kraft pulp or sulfite pulp; bleached or unbleached high-yield pulps such as wood pulp, mechanical pulp or thermomechanical pulp; old newspapers, old magazines, corrugated cardboard boxes, or deinked old paper. Alternatively, mixtures of the above pulp raw materials with synthetic fibers such as asbestos, polyamide, polyimide, polyester, polyolefin, and polyvinyl alcohol can also be used.

[0074] Sizing agents can be added to improve the water resistance of the paper. Examples of sizing agents include cationic sizing agents, anionic sizing agents, and rosin-based sizing agents (e.g., acidic rosin-based sizing agents and neutral rosin-based sizing agents). The amount of sizing agent relative to the pulp can be from 0.01 to 5% by weight.

[0075] In papermaking, the following additives may be used as needed, including: starch, modified starch, carboxymethyl cellulose, polyamine polyamine-epiochlorohydrin resin, and other paper strength enhancers, coagulants, fixatives, retention aids, dyes, fluorescent dyes, slime control agents, and defoamers. Starch and modified starch are preferred. Starch, polyvinyl alcohol, dyes, coatings, anti-slip agents, etc. can also be used as needed, and the oil-resistant agent composition can be coated onto the paper using sizing, gate roll coating, Bill-Blade coating, calender, etc.

[0076] In the oil-resistant layer, the amount of hydrocarbon-containing polymer is preferably 0.01 to 2.0 g / m², and more preferably 0.1 to 1.0 g / m². The oil-resistant layer is preferably formed from an oil-resistant agent composition and starch and / or modified starch. The solid content of the paper-grade oil-resistant agent composition in the oil-resistant layer is preferably less than 2 g / m². In the addition process, the oil-resistant agent component is preferably mixed with the pulp in an amount of 0.01 to 50 parts by weight or 0.01 to 30 parts by weight, for example 0.01 to 10 parts by weight, especially 0.2 to 5.0 parts by weight, relative to 100 parts by weight of the pulp forming the paper. In both external and internal additions, the weight ratio of starch and modified starch to hydrocarbon-containing polymers can be from 10:90 to 98:2.

[0077] In addition, even when using a pool-type two-roll sizing process, in which the processing liquid is stored between the rolls and the paper is passed through the processing liquid between the rolls by any roll speed and rolling pressure, the paper can be given oil resistance.

[0078] Hydrocarbon-containing polymers can be nonionic, cationic, anionic, or amphoteric. In the admixture treatment, the paper substrate may contain additives such as sizing agents, paper strength enhancers, coagulants, retention aids, or flocculators. These additives can be nonionic, cationic, anionic, or amphoteric. The ionic charge density of the additives can be -10,000 to 10,000 μeq / g, preferably -4,000 to 8,000 μeq / g, and more preferably -1,000 to 7,000 μeq / g. The additives (solids or active ingredients) such as sizing agents, paper strength enhancers, coagulants, retention aids, or flocculators are generally used in amounts of 0.1 to 10% by weight (e.g., 0.2 to 5.0% by weight) relative to the pulp. In the case of paper substrates containing cationic additives (e.g., sizing agents, paper strength enhancers, coagulants, retention aids, or flocculators), the oil-resistant agent composition is preferably anionic.

[0079] In the internal processing, it is preferable to process paper from a pulp liquor with a pulp concentration of 0.1 to 5.0% by weight (e.g., 0.3 to 4.0% by weight). Additives (e.g., sizing agents, paper strength enhancers, coagulants, retention aids, or flocculating agents) and hydrocarbon-containing polymers can be added to the pulp liquor. Since pulp is generally anionic, the additives and hydrocarbon-containing polymers are well fixed to the paper in such a way that at least one of the additives and hydrocarbon-containing polymers is preferably cationic or amphoteric. Preferably, the following combinations are used: a combination where the additives are cationic or amphoteric and the hydrocarbon-containing polymer is anionic; a combination where the additives are anionic and the hydrocarbon-containing polymer is cationic or amphoteric; and a combination where the additives and hydrocarbon-containing polymers are cationic or amphoteric. It is preferable to set the ionic charge density of additives such as sizing agents, paper strength enhancers, coagulants, retention aids or flocculators to -1000 to 7000 μeq / g for papermaking, and even more preferably to set the ionic charge density to 100 to 1000 μeq / g (e.g. 330 μeq / g, 420 μeq / g or 680 μeq / g) for papermaking.

[0080] Examples of additives (such as sizing agents, paper strength enhancers, coagulants, retention aids, or coagulants) include: alkyl ketene dimers (AKD), alkenyl succinic anhydride (ASA), styrene-based polymers (styrene / maleic acid polymers, styrene / acrylic acid polymers), urea-formaldehyde polymers, polyethyleneimine, melamine-formaldehyde polymers, polyamide-epimyl chloride polymers, polyacrylamide polymers, polyamine polymers, chlorinated polydiallyl dimethylammonium, alkylamine-epimyl chloride condensates, dichloroethane and polyalkylene polyamine condensates, dicyandiamine-formaldehyde condensates, dimethyldiallyl chloride polymers, and olefin / maleic anhydride polymers. Examples of polyacrylamide polymers include: nonionic polyacrylamide polymers, anionic polyacrylamide polymers, and amphoteric polyacrylamide polymers.

[0081] The oil-resistant agent composition is mixed into a substrate, such as resin or paper, and imparts oil resistance to the substrate.

[0082] When the oil-resistant agent is an internal treatment agent, it can impart oil resistance to the resin, such as a thermoplastic resin, by adding it to the resin. The oil-resistant agent can be used when manufacturing molded resin articles. A polymer is obtained by removing the liquid medium or the liquid medium and emulsifier from a liquid (solution or dispersion) containing a polymer. For example, a polymer can be obtained by redepositing the polymer dispersion (aqueous dispersion or organic solvent dispersion) with water or an organic solvent and then drying it.

[0083] For example, a molded article can be manufactured by a manufacturing method having the following steps: mixing resin and polymer to obtain a resin composition, and molding the resin composition. Preferably, the molded article is manufactured by melt mixing using an extruder or the like. Generally, thermoplastic resins and polymers are compatible in the molten state. Mixing can be carried out using conventional methods such as uniaxial extruders, biaxial extruders, and rollers. The resulting resin composition is then shaped by extrusion molding, injection molding, compression molding, blow molding, compression molding, etc. The resin composition is shaped into various forms. After molding, the resulting molded articles can be further heat-treated in ovens, drying furnaces, etc. Molded articles can be single-layered or multi-layered, such as 3 to 5 layers.

[0084] The substrate can be paper, especially pulp mold. Pulp molds can be manufactured by filling a mold with a pulp slurry containing an oil-resistant agent and allowing water to permeate to the outside of the mold to shape the pulp. Alternatively, injection molding can be used as the forming method. Pulp molds are manufactured by filling the cavity of a permeable mold for pulp molds with papermaking slurry and allowing water to permeate to the outside of the mold. Methods for permeating water from the pulp slurry to the outside of the mold include: allowing water to permeate naturally under normal pressure, and forcing water to permeate by depressurizing the outside of the mold. In injection molding, a molding material containing pulp, starch, water, and an oil-resistant agent is injection molded to obtain a three-dimensional structure (pulp mold).

[0085] The conductivity of the pulp (with added oil-resistant components) can be 0.1 to 2000 μS / cm, 0.1 to 1000 μS / cm, 1 to 800 μS / cm, or 10 to 500 μS / cm. High oil resistance is achieved within this range. Conductivity can be measured using, for example, LAQUAtwin AS-EC-33 manufactured by AS ONE. The optimal pH of the pulp is 4 to 9, more preferably 5 to 8, and even more preferably 6 to 7. Within this range, high oil resistance is achieved. The water used in the pulping solution preferably has a hardness of 5000 ppm or less, more preferably 3000 ppm or less, even more preferably 1000 ppm or less, and most preferably 500 ppm or less. Within this range, high oil resistance can be obtained.

[0086] Molded parts can be used in applications involving thermoplastic resins, especially those requiring excellent ease of cleaning and resistance to damage. Applications include: automotive (exterior and interior parts) (e.g., bumpers, dashboards, door panels), home appliances (e.g., washing machines and refrigerators) (e.g., frames, refrigerator doors, trays, vegetable compartment containers), various shells, buildings (interior and parts) (e.g., handrails, wallpaper, tables, chairs, toilet seats and lids, bathtubs), electronic equipment (e.g., smartphone frames), drains, pipes, tableware, flooring, fuel tanks, fuel lines, OA machines, etc. Among these, automotive interior parts, home appliance interior parts, and buildings are particularly preferred. The preferred method is to add the oil-resistant agent component to the thermoplastic resin and mix the oil-resistant agent component with the thermoplastic resin (internal treatment).

[0087] In this disclosure, the treatment involves applying an oil-resistant agent composition to the treated article. "Treatment" refers to the application of the oil-resistant agent composition to the treated article through methods such as impregnation, spraying, coating, mixing, or addition. Through treatment, the hydrocarbon-containing polymer, which is the active ingredient of the oil-resistant agent composition, penetrates into the interior of the treated article and / or adheres to its surface. The hydrocarbon-containing polymer adheres to the interior and / or surface of the treated article. When the material being treated is, for example, pulp slurry or thermoplastic resin, the treatment causes the hydrocarbon-containing polymer, which is an effective component of the oil-resistant agent, to adhere to the interior and / or surface of the material being treated. [Example]

[0088] The present disclosure is further illustrated by examples, comparative examples, and test examples. However, these descriptions are not intended to limit the scope of the present disclosure. In the following description, unless otherwise specified, parts, % or ratios refer to parts by weight, weight % or weight ratio.

[0089] The test methods used in the following description are as follows.

[0090] [Softening point] The softening point of a polymer is determined by dynamic viscoelasticity (DMA). The aqueous dispersion of the polymer was dried in an oven at approximately 130°C for 30 minutes to obtain the copolymer sample for testing. In the case of an emulsified polymer solution, the polymer and emulsifier were separated by centrifuging at 14000 rpm for 60 minutes in a centrifuge to obtain the copolymer sample for testing. The complex viscosity (η*) of the polymer was measured using a dynamic viscoelasticity measuring device RHEOSOL-G3000 (manufactured by UBM Corporation) at a heating rate of 1°C / min. The temperature at which the complex viscosity reached 1.0 × 10⁴ was set as the softening point.

[0091] [High-temperature oil resistance] Pour 100ml of the evaluation solution (corn oil) at 65°C or 80°C into the molded pulp product shaped into a container. After standing for 30 minutes, pour out the evaluation solution and, following the criteria below, visually evaluate the extent to which the evaluation solution penetrates into the molded pulp product (container). 4: Almost no oil seepage was observed on the inside of the bottom of the container. 3: No oil seepage was observed on the outside of the bottom of the container. 2: Oil seepage was observed on less than 5% of the outer surface area of ​​the bottom of the container. 1: Oil seepage was observed in an area of ​​more than 5% but less than 50% of the outer surface of the bottom of the container. 0: Oil seepage was observed over 50% of the outer surface area of ​​the bottom of the container.

[0092] [High-temperature water resistance] 100 ml of 100°C evaluation solution (water) is injected into the molded pulp product shaped into a container. After standing for 30 minutes, the evaluation solution is poured out. The degree of penetration of the evaluation solution into the molded pulp product (container) is evaluated visually according to the following criteria. 4: Almost no leakage was observed on the inside of the bottom of the container. 3: No leakage was observed on the outside of the bottom of the container. 2: Leakage was observed in less than 5% of the outer surface area of ​​the bottom of the container. 1: Leakage was observed in an area of ​​more than 5% but less than 50% of the outer surface of the bottom of the container. 0: Leakage was observed in more than 50% of the outer surface area of ​​the bottom of the container.

[0093] <Synthesis example 1> 90 parts of stearamide ethyl acrylate, 3 parts of dimethylaminoethyl methacrylate (DM), 7 parts of hydroxybutyl acrylate (HBA), 370 parts of purified water, 1.1 parts of acetic acid, and 10 parts of alkylbis(2-hydroxyalkyl)methylammonium chloride were added to a 1L plastic container. The mixture was heated to 80°C and stirred at 2000 rpm for 1 minute using a homogenizer, followed by emulsification and dispersion by ultrasound for 15 minutes. The emulsion dispersion was transferred to a 1000cc four-necked flask equipped with a nitrogen inlet tube, thermometer, stir bar, and reflux tube. After nitrogen substitution, 1 part of 2,2'-azobis(2-methylpropanediamine) dihydrochloride was added, and the reaction was carried out at 60°C for 4 hours to obtain an aqueous dispersion of the polymer. Then, purified water was added to prepare an aqueous dispersion with a solids concentration of 20% by weight. The ionic charge density of the aqueous dispersion was 250 μeq / g.

[0094] 〈Synthesis example 2〉 90 parts of stearyl acrylate, 3 parts of dimethylaminoethyl methacrylate (DM), 7 parts of hydroxybutyl acrylate (HBA), 290 parts of purified water, 0.8 parts of acetic acid, 7 parts of alkylbis(2-hydroxyalkyl)methylammonium chloride, and 3 parts of polyoxyethylene ethyl ether were added to a 1L plastic container. The mixture was heated to 80°C and stirred at 2000 rpm for 1 minute using a homogenizer, followed by emulsification and dispersion by ultrasound for 15 minutes. The emulsion dispersion was transferred to a 1000cc four-necked flask equipped with a nitrogen inlet tube, thermometer, stir bar, and reflux tube. After nitrogen substitution, 1 part of 2,2'-azobis(2-methylpropanediamine) dihydrochloride was added, and the reaction was carried out at 60°C for 4 hours to obtain an aqueous dispersion of the polymer. Then, purified water was added to prepare an aqueous dispersion with a solids concentration of 25% by weight. The ionic charge density of the aqueous dispersion was 230 μeq / g.

[0095] <Synthesis example 3> 90 parts of stearamide ethyl acrylate, 3 parts of dimethylaminoethyl methacrylate (DM), 7 parts of hydroxybutyl acrylate (HBA), and 100 parts of butanone (MEK) were added to a 500 ml four-necked flask equipped with a nitrogen inlet tube, thermometer, stir bar, and reflux tube. After nitrogen substitution, 0.9 parts of trimethylperoxyethyl acetate (TGE) were added, and the reaction was carried out at 65 °C for 12 hours to obtain a copolymer solution containing the polymer. As a post-treatment, 71 g of a 0.4% acetic acid aqueous solution was added to 50 g of the obtained copolymer solution for dispersion. MEK was then removed by distillation under heating and reduced pressure using an evaporator to obtain a light brown copolymer aqueous dispersion (with a volatile organic solvent content of less than 1% by weight). Pure water was then added to prepare an aqueous dispersion with a solids concentration of 20% by weight. The ionic charge density of the aqueous dispersion was 210 μeq / g.

[0096] 〈Synthesis Example 4〉 90 parts of stearyl acrylate, 3 parts of dimethylaminoethyl methacrylate (DM), 7 parts of hydroxybutyl acrylate (HBA), 290 parts of purified water, 0.8 parts of acetic acid, 7 parts of alkyl dimethyl benzyl ammonium chloride, and 10 parts of polyoxyethylene ethyl ether were added to a 1L plastic container. The mixture was heated to 80°C and stirred at 2000 rpm for 1 minute using a homogenizer, followed by emulsification and dispersion by ultrasound for 15 minutes. The emulsion dispersion was transferred to a 1000cc four-necked flask equipped with a nitrogen inlet tube, thermometer, stir bar, and reflux tube. After nitrogen substitution, 1 part of 2,2'-azobis(2-methylpropanediamine) dihydrochloride was added, and the reaction was carried out at 60°C for 4 hours to obtain an aqueous dispersion of the polymer. Then, purified water was added to prepare an aqueous dispersion with a solids concentration of 25% by weight. The ionic charge density of the aqueous dispersion was 220 μeq / g.

[0097] <Comparative Synthesis Example 1> 78 parts of stearamide ethyl acrylate, 6 parts of dimethylaminoethyl methacrylate (DM), 16 parts of hydroxybutyl acrylate (HBA), 370 parts of purified water, 2.2 parts of acetic acid, and 10 parts of alkylbis(2-hydroxyalkyl)methylammonium chloride were added to a 1L plastic container. The mixture was heated to 80°C and stirred at 2000 rpm for 1 minute using a homogenizer, followed by emulsification and dispersion by ultrasound for 15 minutes. The emulsion dispersion was transferred to a 1000cc four-necked flask equipped with a nitrogen inlet tube, thermometer, stir bar, and reflux tube. After nitrogen substitution, 1 part of 2,2'-azobis(2-methylpropanediamine) dihydrochloride was added, and the reaction was carried out at 60°C for 4 hours to obtain an aqueous dispersion of the polymer. Then, purified water was added to prepare an aqueous dispersion with a solids concentration of 20% by weight. The ionic charge density of the aqueous dispersion was 370 μeq / g.

[0098] <Comparative Synthesis Example 2> 78 parts of stearamide ethyl acrylate, 6 parts of dimethylaminoethyl methacrylate (DM), 16 parts of hydroxybutyl acrylate (HBA), and 100 parts of butanone (MEK) were added to a 500 ml four-necked flask equipped with a nitrogen inlet tube, thermometer, stir bar, and reflux tube. After nitrogen substitution, 0.9 parts of trimethylperoxyethyl acetate (TGE) were added, and the reaction was carried out at 65 °C for 12 hours to obtain a copolymer solution containing the polymer. As a post-treatment, 142 g of a 0.4% acetic acid aqueous solution was added to 50 g of the obtained copolymer solution for dispersion. MEK was then removed by distillation under heating and reduced pressure using an evaporator to obtain a light brown copolymer aqueous dispersion (with a volatile organic solvent content of less than 1% by weight). Pure water was then added to prepare an aqueous dispersion with a solids concentration of 20% by weight. The ionic charge density of the aqueous dispersion was 350 μeq / g.

[0099] <Example 1> While stirring and mixing, 2000g of a 0.5% by weight aqueous dispersion of a mixture of 70 parts of hardwood bleached kraft pulp and 30 parts of softwood bleached kraft pulp with a filterability of 550cc (Canadian Freeness) was added. Then, 0.3g of a 5% solids aqueous solution of alkyl ketene dimer (AKD) (Hercon (registered trademark) 79 manufactured by Solenis) as a sizing agent was added, and stirring was continued for 1 minute. Then, 3.5g of the aqueous dispersion of Synthetic Example 1 was diluted with water to a solids content of 10%, and stirring was continued for 1 minute.

[0100] The aforementioned pulp slurry is placed in a metal tank. At the bottom of this tank, with a mesh placed above it, lies a metal pulp forming mold with numerous suction holes. Using a vacuum pump, the pulp containing aqueous components is suctioned / dehydrated from the opposite side of the pulp forming mold and the mesh, causing the solids (pulp, etc.) contained in the aqueous components to accumulate on the mesh, resulting in a pulp intermediate. The obtained pulp intermediate is then pressurized and dried from above and below using a metal male and female forming mold heated to 60 to 200°C. This produces a pulp molded product shaped into a container. Table 1 presents the ratio of each component in the obtained pulp molded product to the pulp content, and the results of evaluating its high-temperature oil resistance and high-temperature water resistance.

[0101] <Example 2> Except for the absence of alkyl ketene dimer (AKD), the experiments were conducted in the same manner as in Example 1. The proportions of each component in the resulting pulp molded products relative to the pulp content, as well as the results of evaluating high-temperature oil resistance and high-temperature water resistance, are presented in Table 1.

[0102] <Example 3> Except for using the aqueous dispersion of Synthetic Example 2, the experiments were conducted in the same manner as in Example 1. The proportions of each component in the obtained pulp molded products relative to the pulp content, as well as the results of evaluating high-temperature oil resistance and high-temperature water resistance, are presented in Table 1.

[0103] <Example 4> Except for the addition of 2g of water to dilute the aqueous dispersion of Synthetic Example 2 to 10% solids, and 1.0g of water to dilute the amphoteric PAM to 10% solids, the experiments were conducted in the same manner as in Example 3. The proportions of each component in the resulting pulp molded products relative to the pulp content, as well as the results of evaluating high-temperature oil resistance and high-temperature water resistance, are presented in Table 1.

[0104] <Example 5> Except for the absence of alkyl ketene dimer (AKD), the experiments were conducted in the same manner as in Example 3. The proportions of each component in the resulting pulp molded products relative to the pulp content, as well as the results of evaluating high-temperature oil resistance and high-temperature water resistance, are presented in Table 1.

[0105] <Example 6> Except for the absence of alkyl ketene dimer (AKD), the experiments were conducted in the same manner as in Example 4. The proportions of each component in the resulting pulp molded products relative to the pulp content, as well as the results of evaluating high-temperature oil resistance and high-temperature water resistance, are presented in Table 1.

[0106] <Example 7> Except for using the aqueous dispersion of Synthetic Example 3, the experiments were conducted in the same manner as in Example 1. The proportions of each component in the obtained pulp molded products relative to the pulp content, as well as the results of evaluating high-temperature oil resistance and high-temperature water resistance, are presented in Table 1.

[0107] <Example 8> Except for using the aqueous dispersion of Synthetic Example 4, the experiments were conducted in the same manner as in Example 3. The proportions of each component in the obtained pulp molded products relative to the pulp content, as well as the results of evaluating high-temperature oil resistance and high-temperature water resistance, are presented in Table 1.

[0108] <Example 9> Except for the absence of alkyl ketene dimer (AKD), the experiments were conducted in the same manner as in Example 8. The proportions of each component in the resulting pulp molded products relative to the pulp content, as well as the results of evaluating high-temperature oil resistance and high-temperature water resistance, are presented in Table 1.

[0109] <Comparative Example 1> Except for using the aqueous dispersion of Comparative Synthesis Example 1, the experiments were conducted in the same manner as in Example 1. The proportions of each component in the obtained pulp molded articles relative to the pulp content, as well as the results of evaluating high-temperature oil resistance and high-temperature water resistance, are presented in Table 1.

[0110] <Comparative Example 2> Except for using the aqueous dispersion of Comparative Synthesis Example 2, the experiments were conducted in the same manner as in Example 1. The proportions of each component in the obtained pulp molded products relative to the pulp content, as well as the results of evaluating high-temperature oil resistance and high-temperature water resistance, are presented in Table 1.

[0111] [Table 1] [Industry applicability]

[0112] The polymer and oil-resistant composition disclosed herein can be used in paper, especially in food containers and food packaging materials.

Claims

1. A paper oil-resistant agent composition, comprising a hydrocarbon-containing polymer and a liquid medium containing water or a mixture of water and an organic solvent, wherein, The hydrocarbon-containing polymer system comprises: (a) repeating units formed by acrylic monomers having a hydrocarbon group having 7 to 40 carbon atoms and an NH group, and (b) repeating units formed by acrylic monomers having a hydrophilic group, and the hydrocarbon-containing polymer system comprises repeating units formed by monomer (a) in an amount of 80% by weight or more relative to the polymer, and the softening point of the aforementioned hydrocarbon-containing polymer is 80°C or more.

2. The paper oil-resistant agent composition as claimed in claim 1, wherein the hydrocarbon-containing polymer has repeating units formed by an acrylic monomer (a) having an NH-containing group between the polymer backbone and the hydrocarbon group.

3. The paper oil-resistant agent composition as described in claim 1 or 2, wherein, Monomer (a) is an amino-containing monomer represented by the following formula: R12-C(=O)-NH-R13-O-R11, where R11 is an organic residual group with an ethylene unsaturated polymerizable group, R12 is a hydrocarbon group with 7 to 40 carbons, and R13 is a hydrocarbon group with 1 to 5 carbons; Monomer (b) is an acrylic monomer with an oxoalkyl hydrophilic group.

4. The paper oil-resistant agent composition as claimed in claim 1 or 2, wherein the hydrocarbon-containing polymer further comprises: repeating units other than monomers (a) and (b) formed by monomers (c) having ethylene carbon-carbon double bonds and anionic or cationic donor groups.

5. The paper oil-resistant agent composition as described in claim 1 or 2, wherein the hydrocarbon-containing polymer is obtained by emulsification polymerization.

6. The paper oil-resistant agent composition as described in claim 1 or 2 further contains at least one emulsifier selected from cationic emulsifiers, nonionic emulsifiers and anionic emulsifiers.

7. The paper oil-resistant agent composition as claimed in claim 4, wherein the amount of repeating units formed by acrylic monomers (a) having hydrocarbon groups is 80 to 99% by weight relative to the polymer, the amount of repeating units formed by acrylic monomers (b) having hydrophilic groups is 1 to 15% by weight relative to the polymer, and the amount of repeating units formed by monomers (c) having anionic or cationic donor groups is 0 to 20% by weight relative to the polymer.

8. The paper oil-resistant agent composition as described in claim 1 or 2 is added to the paper.

9. An oil-resistant paper having a hydrocarbon-containing polymer in a paper oil-resistant agent composition as described in any one of claims 1 to 8 attached to the paper.

10. The greaseproof paper as described in claim 9 is a pulp molded product.

11. The greaseproof paper as described in claim 9 or 10 is a food packaging material or food container.

12. A method for manufacturing paper, comprising manufacturing paper by means of an external or internal treatment of an oil-resistant composition for paper as described in any one of claims 1 to 8.

13. A method for manufacturing a pulp mold, comprising: filling a mold with an oil-resistant paper composition as described in any one of claims 1 to 8 and a pulp slurry, and allowing water to pass through the outside of the mold to form pulp.