Oil-resistant composition

Abstract

To provide: an oil-resistant agent composition which can provide paper with excellent oil resistance and, when necessary, excellent water resistance; an oil-resistant paper; and a production method of paper.SOLUTION: Provided is an oil-resistant agent composition comprising a hydrocarbon group-containing polymer, the polymer having a repeating unit formed from a monomer containing a C1-40 hydrocarbon group and an NH group-containing group in an amount of 80 or more wt.% relative to the polymer. The hydrocarbon group-containing polymer preferably has (a) a repeating unit formed from an acrylic monomer having a C1-40 hydrocarbon group and an NH group-containing group and (b) a repeating unit formed from an acrylic monomer having a hydrophilic group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to oil-proofing compositions and paper treated with the oil-proofing compositions. [Background technology]

[0002] Food packaging materials and food containers made of paper are required to prevent the seepage of moisture and oil from food, and therefore greaseproofing agents are applied to the paper either internally or externally.

[0003] Patent Document 1 (WO2020 / 054856) discloses an oil-proofing agent for paper comprising a non-fluorine copolymer having (a) repeating units formed from an acrylic monomer having a long-chain hydrocarbon group with 7 to 40 carbon atoms, and (b) repeating units formed from an acrylic monomer having a hydrophilic group. Patent Document 2 (WO2020 / 241709) discloses that high-temperature oil resistance is imparted by a non-fluorinated polymer and inorganic or organic particles. Patent Document 3 (JP 2018-16902 A) discloses a water repellent for paper containing a polymer containing, as a polymerization component, a vinyl monomer having a long-chain alkyl group having 14 or more carbon atoms. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] WO2020 / 054856 publication [Patent Document 2] WO2020 / 241709 publication [Patent Document 3] Japanese Patent Application Publication No. 2018-16902 Summary of the Invention [Problem to be solved by the invention]

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

[0006] The oil-proofing composition of the present disclosure comprises a hydrocarbon group-containing polymer (i.e., a non-fluorinated polymer). The hydrocarbon group-containing polymer preferably has 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. In the hydrocarbon group-containing polymer, an NH group-containing group is preferably present between the polymer main chain and the hydrocarbon group having 1 to 40 carbon atoms. The hydrocarbon group-containing polymer is preferably polyolefin, polyacrylic, polyester, polyamide, polycarbonate, or polyurethane.

[0007] The hydrocarbon group-containing polymer preferably has a softening point of 65°C or higher. The softening point of the hydrocarbon group-containing polymer may be 65° C. or higher, 66° C. or higher, 68° C. or higher, 70° C. or higher, 72° C. or higher, 74° C. or higher, 76° C. or higher, 78° C. or higher, 80° C. or higher, 82° C. or higher, 84° C. or higher, 86° C. or higher, 88° C. or higher, 90° C. or higher, 92° C. or higher, 94° C. or higher, 96° C. or higher, 98° C. or higher, or 100° C. The upper limit of the softening point of the hydrocarbon group-containing polymer may be 210° C., 200° C., 190° C., 180° C., 150° C., 140° C., 130° C., 120° C., or 110° C. "Softening point" refers to the complex viscosity of a polymer measured by dynamic mechanical analysis (DMA) of 1.0x10 4 means the temperature at which

[0008] The hydrocarbon group-containing polymer is a polymer having a hydrocarbon group having 1 to 40 carbon atoms, particularly 3 to 40 or 7 to 40 carbon atoms.

[0009] A preferred embodiment of the invention is as follows. Aspect 1: An oil-proofing composition comprising 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. Aspect 2: The oil-proofing composition according to Aspect 1, wherein the hydrocarbon group-containing polymer is a polyolefin, polyacrylic, polyester, polyamide, polycarbonate, or polyurethane, in which an NH group-containing group is present between the polymer main chain and the hydrocarbon group. Aspect 3: 3. The oil-resistant composition according to claim 1 or 2, wherein the hydrocarbon group-containing polymer has a repeating unit formed from an ethylenic carbon-carbon double bond monomer having an NH group-containing group between the polymer main chain and the hydrocarbon group. Aspect 4: The hydrocarbon group-containing polymer is (a) a repeating unit formed from an acrylic monomer having a hydrocarbon group having 1 to 40 carbon atoms and an NH group-containing group, and (b) Repeating units formed from acrylic monomers having hydrophilic groups 4. The oil-proofing agent composition according to any one of Aspects 1 to 3, comprising: Aspect 5: The hydrocarbon group-containing polymer is A repeating unit formed by a monomer (c) other than the monomers (a) and (b) that has an ethylenic carbon-carbon double bond and an anion-donating group or a cation-donating group. 5. The oil-proofing composition according to claim 4, further comprising: Aspect 6: 6. The oil-resistant composition according to any one of Aspects 1 to 5, wherein the hydrocarbon group-containing polymer has a softening point of 80° C. or higher. Aspect 7: 7. The oil-proofing agent composition according to any one of Aspects 1 to 6, wherein the hydrocarbon group-containing polymer is obtained by emulsion polymerization. Aspect 8: Aspect 8. The oil-proofing composition according to any one of Aspects 1 to 7, further comprising at least one emulsifier selected from the group consisting of cationic emulsifiers, nonionic emulsifiers, and anionic emulsifiers. Aspect 9: Aspects 9. The oil-proofing agent composition according to any one of Aspects 5 to 8, wherein the amount of repeating units formed by the acrylic monomer (a) having a hydrocarbon group is 80 to 99 wt % based on the weight of the polymer, the amount of repeating units formed by the acrylic monomer (b) having a hydrophilic group is 1 to 15 wt % based on the weight of the polymer, and the amount of repeating units formed by the monomer (c) having an anion-donating group or a cation-donating group is 0 to 20 wt % based on the weight of the polymer. Aspect 10: 10. The oil-proofing agent composition according to any one of embodiments 1 to 9, further comprising a liquid medium which is water or a mixture of water and an organic solvent. Aspect 11: 11. Grease-resistant paper having the hydrocarbon group-containing polymer in the oil-proofing agent composition according to any one of Aspects 1 to 10 adhered to the paper. Aspect 12: 12. The greaseproof paper according to claim 11, which is a pulp-molded product. Aspect 13: 13. The greaseproof paper according to embodiment 11 or 12, which is a food packaging material or a food container. Aspect 14: A method for producing paper, comprising treating paper with the oil-proofing agent composition according to any one of aspects 1 to 10 by external or internal addition. Aspect 15: Aspect 15. The method according to aspect 14, wherein the pulp slurry has an electric conductivity of 0.1 to 2000 μS / cm, a pH of 4 to 9, and a hardness of water used in the pulp slurry of 5000 ppm or less. Aspect 16: A method for producing a pulp mold, comprising filling a mold with the oil-proofing agent composition according to any one of aspects 1 to 10 and a pulp slurry, and allowing water to permeate out of the mold to form pulp. [Effects of the Invention]

[0010] According to the present disclosure, excellent oil resistance and water resistance are imparted to 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. DETAILED DESCRIPTION OF THE INVENTION

[0011] The hydrocarbon group-containing polymer has a hydrocarbon group having 1 to 40 carbon atoms and is polyolefin, polyacrylic, polyester, polyamide, polycarbonate, or polyurethane. The hydrocarbon group-containing polymer is preferably a polymer in which ethylenic carbon-carbon double bonds are polymerized. The hydrocarbon group-containing polymer preferably has a repeating unit derived from a monomer having a hydrocarbon group having a carbon number of 1 to 40. It is preferable that an NH group-containing group is present between the polymer main chain and the hydrocarbon group.

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

[0013] Preferred hydrocarbon group-containing polymers are (a) a repeating unit formed by an acrylic monomer having a hydrocarbon group having 1 to 40 carbon atoms and an NH group-containing group, and (b) Repeating units formed by acrylic monomers having hydrophilic groups It has.

[0014] Furthermore, the hydrocarbon group-containing polymer may further comprise, in addition to the monomers (a) and (b), (c) Monomers with ion-donating groups It is preferred that the repeating unit be formed by the following formula: The hydrocarbon group-containing polymer comprises, in addition to the monomers (a), (b), and (c): (d) Other monomers The repeating unit may be formed by the following formula:

[0015] (a) Acrylic monomer having a hydrocarbon group 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 linear or branched hydrocarbon group having 1 to 40 carbon atoms. Since high oil resistance can be obtained, the number of carbon atoms in the hydrocarbon group is preferably 10 to 40, for example, 12 to 30, particularly 15 to 30. Alternatively, the number of carbon atoms in the hydrocarbon group may be 18 to 40.

[0016] The acrylic monomer (a) having a hydrocarbon group is represented by the formula: CH2=C(-X 1 )-C(=O)-Y 1 -Z(-Y 2 -R 1 ) n [In the formula, R 1 are each independently a hydrocarbon group having 1 to 40 carbon atoms, X 1 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y 1 is -O- or -NH-, Y 2 is an NH group-containing group, Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms; n is 1 or 2. It is preferable that the compound is a compound represented by the following formula (acrylate monomer or acrylamide monomer):

[0017] X 1 X 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. 1 Examples of X are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, and a cyano group. 1 is preferably a hydrogen atom, a methyl group, or a chlorine atom. 1 is particularly preferably a hydrogen atom.

[0018] Y 1 is —O— or —NH—, and is preferably —O—.

[0019] Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms. Z may have a linear or branched structure. Z preferably has 2 to 4 carbon atoms, particularly 2. Specific examples of Z include a direct bond, -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH2CH= having a branched structure, -CH2(CH-)CH2- having a branched structure, -CH2CH2CH= having a branched structure, -CH2CH2CH2CH2CH= having a branched structure, -CH2CH2(CH-)CH2- having a branched structure, and -CH2CH2CH2CH= having a branched structure. Z is preferably a divalent hydrocarbon group having 1 to 5 carbon atoms.

[0020] Y 2 is an NH group-containing group (spacer group). Y 2 Y forms a spacer moiety capable of forming hydrogen bonds in the polymer. It is believed that hydrogen bonds are formed by the NH groups in the polymer, improving oil resistance. 2 is preferably an amide group, a urethane group, a urea group, or a sulfonamide group. That is, the NH group-containing group is preferably -NH-C(=O)-, -C(=O)-NH-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -NH-S(=O)2-, or -S(=O)2-NH-.

[0021] n is 1 or 2, but is preferably 1.

[0022] Preferred examples of the acrylic monomer (a), which is an acrylate monomer having a divalent Z group, are: CH2=C(-X 1 )-C(=O)-O-(CH2) m -NH-C(=O)-R 1 , CH2=C(-X 1 )-C(=O)-O-(CH2) m -C(=O)-NH-R1 , CH2=C(-X 1 )-C(=O)-O-(CH2) m -OC(=O)-NH-R 1 , CH2=C(-X 1 )-C(=O)-O-(CH2) m -NH-C(=O)-OR 1 , CH2=C(-X 1 )-C(=O)-O-(CH2) m -NH-C(=O)-NH-R 1 , CH2=C(-X 1 )-C(=O)-O-(CH2) m -NH-S(=O)2-R 1 , CH2=C(-X 1 )-C(=O)-O-(CH2) m -S(=O)2-NH-R 1 CH2=C(-X 1 )-C(=O)-O-(CH2) m -NH-C(=O)-R 1 is particularly preferred. [In the above formula, X 1 and R 1 has the same meaning as above, and m is 1 to 5.

[0023] Preferred specific examples of the acrylic monomer (a), which is an acrylate monomer having a trivalent Z group, are: TIFF0007783503000001.tif2864 TIFF0007783503000002.tif2966 is.

[0024] The acrylic monomer (a) can be produced by reacting a hydroxyalkyl (meth)acrylate or a hydroxyalkyl (meth)acrylamide with an alkyl isocyanate, such as lauryl isocyanate, myristyl isocyanate, cetyl isocyanate, stearyl isocyanate, oleyl isocyanate, or behenyl isocyanate. Alternatively, the acrylic monomer (a) can be produced by reacting a (meth)acrylate having an isocyanate group in the side chain, such as 2-methacryloyloxyethyl isocyanate, with an alkylamine or alkyl alcohol. Examples of alkylamines include laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, and behenylamine. Examples of alkyl alcohols include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and behenyl alcohol.

[0025] The acrylic monomer (a) having a hydrocarbon group is, for example, X 1 is preferably an acrylate in which is a hydrogen atom.

[0026] The acrylic monomer (a) is represented by the formula: R 12 -C(=O)-NH-R 13 -OR 11 [In the formula, R 11 represents an organic residue having an ethylenically unsaturated polymerizable group, R 12 is a hydrocarbon group having 1 to 40 carbon atoms, R 13 is a hydrocarbon group having 1 to 5 carbon atoms. It is preferable that the monomer is an amide group-containing monomer represented by the following formula:

[0027] R 11 is an organic residue having an ethylenically unsaturated polymerizable group, and is not particularly limited as long as it has a carbon-carbon double bond. Specifically, -C(=O)CR 14 =CH2, -CHR14 =CH2, -CH2CHR 14 ═CH2, and the like. 14 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 11 R may have various organic groups in addition to the ethylenically unsaturated polymerizable group, such as chain hydrocarbons, cyclic hydrocarbons, polyoxyalkylene groups, and polysiloxane groups, and these organic groups may be substituted with various substituents. 11 is -C(=O)CR 14 It is preferred that =CH2.

[0028] R 12 R is a hydrocarbon group having 1 to 40 carbon atoms, preferably an alkyl group, and examples thereof include chain hydrocarbon groups and cyclic hydrocarbon groups. Of these, a chain hydrocarbon group is preferred, and a linear saturated hydrocarbon group is particularly preferred. 12 The number of carbon atoms is 1 to 40, preferably 11 to 27, and particularly preferably 15 to 23.

[0029] R 13 R 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. 13 The number of carbon atoms in R is preferably 2 to 4, and particularly preferably 2. 13 is preferably an alkylene group.

[0030] The amide group-containing monomer is R 12 There is only one type (e.g., R 12 (Only compounds with 17 carbon atoms) or R 12 is a combination of multiple 12 and a compound having 17 carbon atoms, R 12 and a compound having 15 carbon atoms).

[0031] An example of an amide group-containing monomer is a carboxylic acid amide alkyl (meth)acrylate. Specific examples of amide group-containing monomers include palmitic acid amidoethyl (meth)acrylate, stearic acid amidoethyl (meth)acrylate, behenic acid amidoethyl (meth)acrylate, myristate amidoethyl (meth)acrylate, laurate amidoethyl (meth)acrylate, isostearate ethyl amido(meth)acrylate, oleic acid ethyl amido(meth)acrylate, tert-butylcyclohexylcaproic acid amidoethyl (meth)acrylate, adamantanecarboxylic acid ethyl amido(meth)acrylate, naphthalenecarboxylic acid amidoethyl (meth)acrylate, anthracenecarboxylic acid amidoethyl (meth)acrylate, palmitic acid amidopropyl (meth)acrylate, stearic acid amidopropyl (meth)acrylate, palmitic acid amidoethyl vinyl ether, stearic acid amidoethyl vinyl ether, palmitic acid amidoethyl allyl ether, stearic acid amidoethyl allyl ether, or mixtures thereof.

[0032] The amide group-containing monomer is preferably stearic acid amidoethyl (meth)acrylate. The amide group-containing monomer may be a mixture containing stearic acid amidoethyl (meth)acrylate. In the mixture containing stearic acid amidoethyl (meth)acrylate, the amount of stearic acid amidoethyl (meth)acrylate may be, for example, 55 to 99 wt %, preferably 60 to 85 wt %, and more preferably 65 to 80 wt %, based on the total weight of the amide group-containing monomers, and the remaining monomer may be, for example, palmitic acid amidoethyl (meth)acrylate.

[0033] (b) Acrylic monomer having a hydrophilic group The acrylic monomer (b) having a hydrophilic group is a monomer other than the monomer (a) and is a hydrophilic monomer. The hydrophilic group is preferably an oxyalkylene group (the alkylene group has 2 to 6 carbon atoms). In particular, the acrylic monomer (b) having a hydrophilic group is preferably a polyalkylene glycol mono(meth)acrylate and / or a polyalkylene glycol di(meth)acrylate, or a polyalkylene glycol mono(meth)acrylamide. The polyalkylene glycol mono(meth)acrylate, polyalkylene glycol di(meth)acrylate, and polyalkylene glycol mono(meth)acrylamide are represented by the general formula: CH2=CX 2 C(=O)-O-(RO) n -X 3 (b1) CH2=CX 2 C(=O)-O-(RO) n -C(=O)CX 2 =CH2(b2), or CH2=CX 2 C(=O)-NH-(RO) n -X 3 (b3) [In the formula, X 2 each independently represents a hydrogen atom or a methyl group, X 3 are each independently a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms. R is an alkylene group having 2 to 6 carbon atoms, n is an integer between 1 and 90 ] Preferably, n is represented by the formula: where 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 may be a linear or branched alkylene group, for example, of the formula -(CH2) x -or-(CH2) x1 -(CH(CH3)) x2 -(CH2) [wherein x1 and x2 are 0 to 6, for example, 2 to 5, and the sum of x1 and x2 is 1 to 6. x1- and -(CH(CH3)) x2 The order of - is not limited to the depicted formula and may be random. -(RO) n In -, R may be two or more types (for example, two to four types, particularly two types), and -(RO) 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.

[0034] In general formulas (b1), (b2), and (b3), R is preferably an ethylene group, a propylene group, or a butylene group. In general formulas (b1), (b2), and (b3), R may be a combination of two or more alkylene groups. In this case, at least one of R is preferably an ethylene group, a propylene group, or a butylene group. Examples of R combinations include an ethylene / propylene combination, an ethylene / butylene combination, and a propylene / butylene combination. Monomer (b) may be a mixture of two or more types. In this case, at least one of the monomers (b) is preferably represented by general formula (b1) or (b2), or (b3), where R is preferably an ethylene group, a propylene group, or a butylene group. Furthermore, when using a polyalkylene glycol di(meth)acrylate represented by general formula (b2), it is not preferable to use it alone as monomer (b), but it is preferable to use it in combination with monomer (b1). In this case, it is also preferable that the compound represented by the general formula (b2) is contained in the monomer (b) used in an amount of less than 30% by weight.

[0035] Specific examples of the acrylic monomer (b) having a hydrophilic group include, but are not limited to, the following: 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) 90 -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)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

[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] The monomer (b) is X 2 is a hydrogen atom. In particular, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or hydroxyethyl acrylamide is preferred.

[0044] (c) Monomers with ion-donating groups The monomer (c) having an ion-donating group is a monomer other than the monomer (a) and the monomer (b). The monomer (c) is preferably a monomer having an ethylenic carbon-carbon double bond and an ion-donating group. The ion-donating group is an anion-donating group and / or a cation-donating group.

[0045] Examples of the monomer having an anion-donating group include a monomer having a carboxyl group, a sulfonic acid group, or a phosphoric acid group. Specific examples of the monomer having an anion-donating 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.

[0046] Salts of anion-donating groups include alkali metal salts, alkaline earth metal salts, and ammonium salts, such as methylammonium salts, ethanolammonium salts, and triethanolammonium salts.

[0047] In the monomer having a cation-donating group, examples of the cation-donating group include an amino group, preferably a tertiary amino group or a quaternary amino group. In the tertiary amino group, the two groups bonded to the nitrogen atom are preferably the same or different and are an aliphatic group (particularly an alkyl group) having 1 to 5 carbon atoms, an aromatic group (an aryl group) having 6 to 20 carbon atoms, or an araliphatic group (particularly an aralkyl group, e.g., a benzyl group (CH-CH-)) 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 and are an aliphatic group (particularly an alkyl group) having 1 to 5 carbon atoms, an aromatic group (an aryl group) having 6 to 20 carbon atoms, or an araliphatic group (particularly an aralkyl group, e.g., a benzyl group (CH-CH-)) having 7 to 25 carbon atoms. In the tertiary amino group and the quaternary amino group, the remaining group bonded to the nitrogen atom may have a carbon-carbon double bond. The cation-donating group may be in the form of a salt.

[0048] The cation-donating 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.

[0049] Specific examples of the monomer having a cation donor 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 -

[0050] As the monomer (c) having an ion-donating group, methacrylic acid, acrylic acid and dimethylaminoethyl methacrylate are preferred, and methacrylic acid and dimethylaminoethyl methacrylate are more preferred.

[0051] (d) Other monomers The other monomer (d) is a monomer other than the monomers (a), (b), and (c). Examples of such other monomers include ethylene, vinyl acetate, vinyl chloride, vinyl fluoride, halogenated vinylstyrene, α-methylstyrene, p-methylstyrene, polyoxyalkylene mono(meth)acrylate, (meth)acrylamide, diacetone (meth)acrylamide, methylolated (meth)acrylamide, N-methylol (meth)acrylamide, alkyl vinyl ether, halogenated alkyl vinyl ether, alkyl vinyl ketone, butadiene, isoprene, chloroprene, glycidyl (meth)acrylate, aziridinyl (meth)acrylate, benzyl (meth)acrylate, isocyanatoethyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, short-chain alkyl (meth)acrylate, maleic anhydride, (meth)acrylates having a polydimethylsiloxane group, and N-vinylcarbazole.

[0052] The amount of repeating units formed by the monomer (a) (repeating units (a)) 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, based on the hydrocarbon group-containing polymer (or based on the total of repeating units (a) and repeating units (b)). The amount of repeating units (repeating units (a)) formed by the monomer (a) 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, based on the hydrocarbon group-containing polymer (or based on the total of repeating units (a) and repeating units (b)).

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

[0054] The weight average molecular weight of the hydrocarbon group-containing polymer may be 1,000 to 10,000,000 or 100,000,000, preferably 5,000 to 8,000,000 or 80,000,000, and more preferably 10,000 to 4,000,000 or 40,000,000. The weight average molecular weight is a value determined by gel permeation chromatography in terms of polystyrene. As used herein, "(meth)acrylic" means acrylic or methacrylic. For example, "(meth)acrylate" means acrylate or methacrylate.

[0055] From the viewpoint of oil resistance, the hydrocarbon group-containing polymer is preferably a random copolymer rather than a block copolymer.

[0056] The polymerization of the hydrocarbon group-containing polymer is not particularly limited, and various polymerization methods can be selected, such as bulk polymerization, solution polymerization, emulsion polymerization, and radiation polymerization. For example, solution polymerization using an organic solvent or emulsion polymerization using water or a combination of an organic solvent and water is generally selected. After polymerization, the polymer is diluted with water and emulsified in water to prepare a treatment liquid. In the present disclosure, after polymerization (e.g., solution polymerization or emulsion polymerization, preferably solution polymerization), water is added and the solvent is removed to disperse the polymer in water. A self-dispersing product can be produced without the need to add an emulsifier. In the present disclosure, emulsion polymerization is preferably used, since emulsion polymerization provides a polymer with superior high-temperature oil resistance compared to solution polymerization for the same monomer composition.

[0057] Examples of organic solvents include ketones such as acetone and methyl ethyl ketone, 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, and alcohols such as ethyl alcohol and isopropanol.

[0058] The polymerization initiator may be, for example, a peroxide, an azo compound, or a persulfate compound. The polymerization initiator is generally water-soluble and / or oil-soluble. Specific preferred examples of the oil-soluble polymerization initiator include 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-isobutyronitrile), benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, and t-butyl perpivalate.

[0059] Specific preferred examples of the water-soluble polymerization initiator include 2,2'-azobisisobutylamidine dihydrochloride, 2,2'-azobis(2-methylpropionamidine) 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, and hydrogen peroxide. The polymerization initiator is used in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the monomer.

[0060] Furthermore, for the purpose of molecular weight control, a chain transfer agent such as a mercapto group-containing compound may be used, specific examples of which include 2-mercaptoethanol, thiopropionic acid, alkyl mercaptan, etc. The mercapto group-containing compound is used in an amount of 10 parts by weight or less, in the range of 0.01 to 5 parts by weight, per 100 parts by weight of the monomer.

[0061] Specifically, the hydrocarbon group-containing polymer can be produced as follows. In solution polymerization, a method is employed in which a monomer is dissolved in an organic solvent, the solvent is purged with nitrogen, a polymerization initiator is added, and the mixture is heated and stirred for 1 to 10 hours at a temperature in the range of 40 to 120° C. The polymerization initiator may generally be an oil-soluble polymerization initiator.

[0062] The organic solvent is one that is inactive to the monomers and dissolves them, and examples of the organic solvent include ketones such as acetone and methyl ethyl ketone, 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 ethyl alcohol and isopropanol, and hydrocarbon solvents such as n-heptane, n-hexane, n-octane, cyclohexane, methylcyclohexane, cyclopentane, methylcyclopentane, methylpentane, 2-ethylpentane, isoparaffin hydrocarbons, liquid paraffin, decane, undecane, dodecane, mineral spirits, mineral turpentine, and naphtha. Preferred examples of the solvent include acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, 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 organic solvent is used in an amount of 50 to 2000 parts by weight, for example, 50 to 1000 parts by weight, per 100 parts by weight of the total of the monomers.

[0063] In emulsion polymerization, a method is employed in which a monomer is emulsified in water in the presence of an emulsifier or the like, and after nitrogen substitution, a polymerization initiator is added and the mixture is polymerized by stirring for 1 to 10 hours at a temperature ranging from 40 to 80° C. The polymerization initiator is a water-soluble polymerization initiator, for example, 2,2′-azobisisobutylamidine dihydrochloride, 2,2′-azobis(2-methylpropionamidine) 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, for example, 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-isobutyronitrile), benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, t-butyl perpivalate The polymerization initiator is used in an amount of 0.01 to 10 parts by weight relative to 100 parts by weight of the monomer.

[0064] To obtain a polymer aqueous dispersion with excellent shelf stability, it is desirable to atomize the monomer in water using an emulsifying device capable of applying powerful crushing energy, such as a high-pressure homogenizer or ultrasonic homogenizer, and then polymerize using an oil-soluble polymerization initiator. Anionic, cationic, or nonionic emulsifiers can be used as emulsifiers, and are used in amounts ranging from 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. Adding a compatibilizer can improve emulsification and copolymerization properties.

[0065] Examples of 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, and isoprene glycol. These may be used in an amount of 1 to 50 parts by weight, e.g., 10 to 40 parts by weight, per 100 parts by weight of water. The addition of NMP, DPM, 3-methoxy-3-methyl-1-butanol, or isoprene glycol (preferably in an amount of 1 to 20% by weight, particularly 3 to 10% by weight, based on the composition) improves the stability of the composition (especially emulsions). 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, e.g., 10 to 40 parts by weight, based on 100 parts by weight of the total amount of monomers.

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

[0067] The ionic charge density of the oil proofing composition may be -5000 μeq / g or more, -2500 μeq / g or more, -1500 μeq / g or more, -500 μeq / g or more, 0 μeq / g or more, 100 μeq / g or more, or 200 μeq / g or more, preferably -2500 μeq / g or more, more preferably -400 μeq / g or more, for example 0 μeq / g or more. The ionic charge density of the oil proofing composition may be 7500 μeq / g or less, 5000 μeq / g or less, 2500 μeq / g or less, 1000 μeq / g or less, 500 μeq / g or less, 350 μeq / g or less, 300 μeq / g or less, or 250 μeq / g or less, preferably 5000 μeq / g or less, more preferably 800 μeq / g or less, for example 300 μeq / g or less. In particular, the ionic charge density of the oil-proofing composition is preferably −2500 to 5000 μeq / g, and 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-proofing composition can be measured, for example, by the following method. <Measurement of ionic charge density> The anion demand of a 0.1 g / L sample solution is measured using a particle charge meter (BTG MUTEK PCD-04) with 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 way 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).

[0068]

number

[0069] The organic solvent in the polymer solution can be removed by heating the polymer solution (preferably under reduced pressure) (for example, to 30° C. or higher, for example, 50 to 120° C.).

[0070] The oil-proofing composition can be used to treat (eg, surface treat, internally treat) a paper substrate. The oil-proofing composition can be applied to the object to be treated by a conventionally known method. Typically, the oil-proofing composition is dispersed and diluted in an organic solvent or water, and then applied to the surface of the object to be treated by a known method such as dip coating, spray coating, or foam coating, followed by drying (surface treatment). Alternatively, the oil-proofing composition is added to a pulp slurry, which is then dehydrated, molded, and dried by a known method (internal addition treatment). Examples of the paper substrate to be treated include paper, paper containers, and paper molded articles (for example, pulp molds). The hydrocarbon group-containing polymers of the present disclosure adhere well to paper substrates.

[0071] The paper can be produced by a conventional papermaking method. An internal treatment method in which the oil-proofing composition is added to the pulp slurry before papermaking, or an external treatment method in which the oil-proofing composition is applied to the paper after papermaking, can be used. The internal treatment method is preferred as the treatment method for the oil-proofing composition in the present disclosure.

[0072] The size press for external addition treatment can be divided into the following types depending on the application method: One application method is the so-called pond-type two-roll size press, in which the coating liquid (size liquid) is supplied to the nip formed by passing the paper between two rubber rolls, creating a pool of coating liquid called a pond. The paper is then passed through this pool of coating liquid 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 mold, and the rod metering size press. In the pond-type two-roll size press, the size liquid tends to penetrate into the paper, while in the surface transfer type, the size liquid components tend to remain on the surface of the paper. Compared to the pond-type two-roll size press, the surface transfer type allows the coating layer to remain on the surface of the paper more easily, and a larger oil-resistant layer is formed on the surface than with the pond-type two-roll size press. In the present disclosure, oil resistance can be imparted to paper even when the former pond-type two-roll size press is used. Papers treated in this way, after simple drying at room temperature or at elevated temperature, 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 nature of the paper, exhibit excellent oil and water resistance.

[0073] The present disclosure can be used in gypsum board base paper, coated base paper, medium paper, general liners and corrugating media, neutral pure white roll paper, neutral liners, anti-rust liners and metal interleaving paper, kraft paper, etc. It can also be used in 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.

[0074] Pulp raw materials that can be used include bleached or unbleached chemical pulps such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulps such as groundwood pulp, mechanical pulp or thermomechanical pulp, and recycled paper pulp such as recycled newspapers, recycled magazines, recycled corrugated cardboard, and deinked recycled paper. Mixtures of the above pulp raw materials with synthetic fibers such as asbestos, polyamide, polyimide, polyester, polyolefin, and polyvinyl alcohol can also be used.

[0075] A sizing agent can be added to improve the water resistance of 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 may be 0.01 to 5% by weight of the pulp.

[0076] If necessary, the paper may contain additives used in paper production, such as paper strength agents such as starch, modified starch, carboxymethyl cellulose, and polyamide polyamine-epichlorohydrin resin, flocculants, fixing agents, retention aids, dyes, fluorescent dyes, slime control agents, and antifoaming agents, in amounts commonly used in papermaking. Starch and modified starch are preferably used. If necessary, the oil-proofing composition can be applied to the paper using starch, polyvinyl alcohol, dye, coating color, anti-slip agent, etc., by a size press, gate roll coater, bill blade coater, calender, etc.

[0077] In the case of external addition, the amount of hydrocarbon group-containing polymer contained in the oil-resistant layer is 0.01 to 2.0 g / m 2 , especially 0.1 to 1.0 g / m 2 The oil-resistant layer is preferably formed from an oil-proofing composition and starch and / or modified starch. The solid content of the oil-proofing composition for paper in the oil-resistant layer is preferably 2 g / m 2 It is preferable that: In the internal addition, the oil-proofing composition is preferably mixed with the pulp so that the amount of the oil-proofing composition is 0.01 to 50 parts by weight or 0.01 to 30 parts by weight, for example 0.01 to 10 parts by weight, particularly 0.2 to 5.0 parts by weight, per 100 parts by weight of the pulp forming the paper. In the external addition and internal addition, the weight ratio of starch or modified starch to the hydrocarbon group-containing polymer may be 10:90 to 98:2.

[0078] In external addition, oil resistance can also be imparted to paper using a so-called pond-type two-roll size press process, in which a treatment solution is stored between rolls and the base paper is passed through the treatment solution between the rolls at any roll speed and nip pressure.

[0079] The hydrocarbon group-containing polymer may be nonionic, cationic, anionic, or amphoteric. In the external additive treatment, the paper substrate may contain additives such as sizing agents, paper strength agents, flocculants, retention agents, or coagulants. The additives may be nonionic, cationic, anionic, or amphoteric. The ionic charge density of the additives may 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. Additives such as sizing agents, paper strength agents, flocculants, retention agents, or coagulants (solids or active ingredients) can generally be used in an amount of 0.1 to 10% by weight (e.g., 0.2 to 5.0% by weight) based on the pulp. In the case of a paper substrate containing a cationic additive (e.g., a sizing agent, paper strength agent, flocculant, retention agent, or coagulant), the oil-proofing agent composition is preferably anionic.

[0080] In the internal addition treatment, it is preferable to make paper from a pulp slurry having 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 agents, flocculants, retention agents, or coagulants) and a hydrocarbon group-containing polymer can be added to the pulp slurry. Because pulp is generally anionic, it is preferable that at least one of the additive and the hydrocarbon group-containing polymer be cationic or amphoteric so that the additive and the hydrocarbon group-containing polymer are well fixed to the paper. It is preferable to use a combination in which the additive is cationic or amphoteric and the hydrocarbon group-containing polymer is anionic, a combination in which the additive is anionic and the hydrocarbon group-containing polymer is cationic or amphoteric, or a combination in which the additive and the hydrocarbon group-containing polymer are cationic or amphoteric. It is more preferable to make paper with an ionic charge density of additives such as sizing agents, paper strength agents, flocculants, retention agents, or coagulants of -1000 to 7000 μeq / g, and even more preferable to make paper with an ionic charge density of 100 to 1000 μeq / g (e.g., 330 μeq / g, 420 μeq / g, or 680 μeq / g).

[0081] Examples of additives (e.g., sizing agents, paper strength agents, flocculants, retention agents, or coagulants) include alkylketene dimers, alkenyl succinic anhydrides, styrene polymers (styrene / maleic acid polymers, styrene / acrylic acid polymers), urea-formaldehyde polymers, polyethyleneimine, melamine-formaldehyde polymers, polyamidoamine-epichlorohydrin polymers, polyacrylamide polymers, polyamine polymers, polydiallyldimethylammonium chloride, alkylamine-epichlorohydrin condensates, condensates of alkylene dichlorides and polyalkylenepolyamines, dicyandiamide-formaldehyde condensates, dimethyldiallylammonium chloride polymers, and olefin / maleic anhydride polymers. Examples of polyacrylamide polymers include nonionic polyacrylamide polymers, anionic polyacrylamide polymers, and amphoteric polyacrylamide polymers.

[0082] The oil-proofing composition is mixed into a substrate, such as a resin or paper, to impart oil resistance to the substrate.

[0083] When the oil-proofing composition is an internal treatment agent, it can impart oil resistance to a resin, for example, a thermoplastic resin, by adding it to the resin. The oil-proofing composition can be used when producing a molded article of the resin. The liquid medium or the liquid medium and the emulsifier are removed from a liquid (solution or dispersion) containing the polymer to obtain a polymer. For example, the polymer can be obtained by reprecipitating a polymer dispersion (aqueous dispersion or organic solvent dispersion) with water or an organic solvent and then drying it.

[0084] For example, a molded article can be produced by a production method including a step of mixing a resin and a polymer to obtain a resin composition, and a step of molding the resin composition. It is preferable to produce a molded article by melt-kneading using an extruder or the like. Generally, thermoplastic resins and polymers are compatible in a molten state. Kneading can be carried out by a conventionally known method, such as using a single-screw extruder, a twin-screw extruder, or a roll. The resin composition thus obtained is molded by extrusion molding, injection molding, compression molding, blow molding, press, or the like. The resin composition is molded into molded articles of various shapes. The molded articles obtained may be further subjected to heat treatment in an oven, a drying furnace, or the like after molding. The molded articles may be single-layered or multi-layered, having 2 to 10 layers, for example, 3 to 5 layers.

[0085] The substrate may be paper, especially molded pulp. The pulp mold can be produced by filling a mold with a pulp slurry containing the oil-proofing composition and allowing water to permeate out of the mold to mold the pulp. Alternatively, injection molding may be used for molding. Pulp molds can be produced by filling the cavity of the water-permeable mold for pulp mold with a papermaking solution and allowing the water to permeate outside the mold. Methods for permeating the water in the pulp slurry outside the mold include a method of allowing the water to permeate naturally at normal pressure and a method of forcing the water to permeate by reducing the pressure outside the mold. In injection molding, a molding material containing pulp, starch, water, and an oil-proofing agent composition is injection molded to obtain a three-dimensional structure (pulp mold).

[0086] The electrical conductivity of the pulp slurry (to which the oil-proofing composition has been added) is preferably 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 can be achieved within this range. The electrical conductivity can be measured, for example, using AS ONE's LAQUAtwin AS-EC-33. The pH of the pulp slurry is preferably 4 to 9, more preferably 5 to 8, and even more preferably 6 to 7. Within this range, high oil resistance can be obtained. The hardness of the water used in the pulp slurry is preferably 5000 ppm or less, more preferably 3000 ppm or less, particularly preferably 1000 ppm or less, and especially preferably 500 ppm or less. When the hardness is within this range, high oil resistance is obtained.

[0087] The molded article can be used in applications where thermoplastic resins are used, particularly applications where excellent wipeability and scratch resistance are preferred. Examples of applications for the molded article include automobiles (exterior and interior parts) (e.g., bumpers, instrument panels, door trims), home electrical appliances (e.g., washing machines and refrigerators) (e.g., housings, refrigerator doors, trays, vegetable compartments), various cases, building interiors and parts (e.g., handrails, wallpaper, desks, chairs, toilet seats and toilet seat restrainers, bathtubs), electronic devices (e.g., smartphone housings), drains, pipes, tableware, flooring, gasoline tanks, fuel hoses, and office equipment. Among these, automotive interior parts, home electrical appliance interior parts, and buildings are particularly preferred. It is preferable to add the oil-proofing composition to the thermoplastic resin and mix the oil-proofing composition with the thermoplastic resin (internal addition treatment).

[0088] In the present disclosure, an article to be treated is treated with an oil-proofing composition. "Treatment" refers to applying the oil-proofing composition to the article to be treated by immersion, spraying, coating, mixing, adding, or the like. The treatment allows the hydrocarbon group-containing polymer, which is the active ingredient of the oil-proofing composition, to penetrate into the interior of the article to be treated and / or adhere to the surface of the article to be treated. The hydrocarbon group-containing polymer adheres to the interior and / or surface of the article to be treated. When the material to be treated is, for example, a pulp slurry or a thermoplastic resin, the hydrocarbon group-containing polymer, which is the active ingredient of the oil-proofing agent composition, adheres to the interior and / or surface of the material to be treated by the treatment. [Example]

[0089] Next, the present disclosure will be specifically described with reference to examples, comparative examples, and test examples, but the present disclosure is not limited to these descriptions. In the following, parts, % or ratios are by weight unless otherwise specified.

[0090] The test methods used below are as follows:

[0091] [Softening point] The softening point of the polymer was determined by dynamic mechanical analysis (DMA). The aqueous dispersion of the polymer was dried in an oven at approximately 130°C for 30 minutes to obtain a sample copolymer for measurement. In the case of an emulsion polymerization solution, 10 g of the aqueous dispersion was dispersed in 20 g of isopropyl alcohol and centrifuged at 14,000 rpm for 60 minutes to separate the polymer and emulsifier, obtaining a sample copolymer for measurement. The complex viscosity (η*) of the polymer was measured using a dynamic viscoelasticity measuring device RHEOSOL-G3000 (UBM Co., Ltd.) at a heating rate of 1°C / min. The complex viscosity was 1.0 x 10 4 The temperature at which this occurs was taken as the softening point.

[0092] [High temperature oil resistance] 100 ml of the 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 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 are visible inside the bottom of the container 3: No oil stains on the outside of the container bottom 2: Oil stains are visible on less than 5% of the outer surface of the container bottom. 1: Oil stains are visible on 5% to less than 50% of the outer surface area of ​​the container bottom. 0: Oil stains are visible on more than 50% of the outer surface of the container bottom

[0093] [High temperature water resistance] 100 ml of the 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 stains are visible inside the bottom of the container 3: No liquid stains are visible on the outside of the container bottom 2: Liquid stains are visible on less than 5% of the outer surface of the container bottom. 1: Liquid stains are visible on 5% to less than 50% of the outer area of ​​the container bottom. 0: Liquid stains are visible on more than 50% of the outer surface area of ​​the container bottom

[0094] <Synthesis Example 1> A 1 L plastic container was charged with 90 parts stearamidoethyl acrylate, 3 parts dimethylaminoethyl methacrylate (DM), 7 parts hydroxybutyl acrylate (HBA), 370 parts pure water, 1.1 parts acetic acid, and 10 parts alkylbis(2-hydroxyalkyl)methylammonium chloride. The mixture was heated to 80 °C, stirred at 2000 rpm with a homomixer for 1 minute, and then ultrasonically emulsified for 15 minutes. The emulsified dispersion was transferred to a 1000 cc four-neck flask equipped with a nitrogen inlet tube, thermometer, stirrer, and reflux tube. After nitrogen substitution, 1 part 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added and reacted at 60 °C for 4 hours to obtain an aqueous polymer dispersion. Pure water was then added to prepare an aqueous dispersion with a solids concentration of 20 wt%. The ionic charge density of the aqueous dispersion was 250 μeq / g.

[0095] <Synthesis Example 2> A 1 L plastic container was charged with 90 parts stearamidoethyl acrylate, 3 parts dimethylaminoethyl methacrylate (DM), 7 parts hydroxybutyl acrylate (HBA), 290 parts pure water, 0.8 parts acetic acid, 7 parts alkylbis(2-hydroxyalkyl)methylammonium chloride, and 3 parts polyoxyethylene alkyl ether. The mixture was heated to 80 °C, stirred at 2000 rpm with a homomixer for 1 minute, 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, stirrer, and reflux condenser. After nitrogen substitution, 1 part 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added and reacted at 60 °C for 4 hours to obtain an aqueous polymer dispersion. Pure water was then added to prepare an aqueous dispersion with a solids concentration of 25 wt%. The ionic charge density of the aqueous dispersion was 230 μeq / g.

[0096] <Synthesis Example 3> A 500 ml four-neck flask equipped with a nitrogen inlet tube, a thermometer, a stirrer, and a reflux condenser was charged with 90 parts of stearamidoethyl acrylate, 3 parts of dimethylaminoethyl methacrylate (DM), 7 parts of hydroxybutyl acrylate (HBA), and 100 parts of methyl ethyl ketone (MEK). After replacing the atmosphere with nitrogen, 0.9 parts of t-butyl peroxypivalate was added and the mixture was allowed to react at 65°C for 12 hours to obtain a polymer copolymer-containing solution. As a post-treatment, 71 g of 0.4% acetic acid aqueous solution was added to 50 g of the obtained copolymer solution and dispersed. After heating using an evaporator, MEK was distilled off under reduced pressure to obtain a light brown copolymer aqueous dispersion (volatile organic solvent content: 1 wt% or less). Purified water was then added to prepare an aqueous dispersion with a solids concentration of 20 wt%. The ionic charge density of the aqueous dispersion was 210 μeq / g.

[0097] <Synthesis Example 4> A 1 L plastic container was charged with 90 parts stearamidoethyl acrylate, 3 parts dimethylaminoethyl methacrylate (DM), 7 parts hydroxybutyl acrylate (HBA), 290 parts pure water, 0.8 parts acetic acid, 7 parts alkyldimethylbenzylammonium chloride, and 10 parts polyoxyethylene alkyl ether. The mixture was heated to 80 °C, stirred at 2000 rpm with a homomixer for 1 minute, and then ultrasonically emulsified for 15 minutes. The emulsified dispersion was transferred to a 1000 cc four-neck flask equipped with a nitrogen inlet tube, thermometer, stirrer, and reflux condenser. After nitrogen substitution, 1 part 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added and reacted at 60 °C for 4 hours to obtain an aqueous polymer dispersion. Pure water was then added to prepare an aqueous dispersion with a solids concentration of 25 wt%. The ionic charge density of the aqueous dispersion was 220 μeq / g.

[0098] <Comparative Synthesis Example 1> A 1 L plastic container was charged with 78 parts stearamidoethyl acrylate, 6 parts dimethylaminoethyl methacrylate (DM), 16 parts hydroxybutyl acrylate (HBA), 370 parts pure water, 2.2 parts acetic acid, and 10 parts alkylbis(2-hydroxyalkyl)methylammonium chloride. The mixture was heated to 80 °C, stirred at 2000 rpm with a homomixer for 1 minute, 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, stirrer, and reflux tube. After nitrogen substitution, 1 part of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added and reacted at 60 °C for 4 hours to obtain an aqueous polymer dispersion. Pure water was then added to prepare an aqueous dispersion with a solids concentration of 20 wt%. The ionic charge density of the aqueous dispersion was 370 μeq / g.

[0099] <Comparative Synthesis Example 2> A 500 ml four-neck flask equipped with a nitrogen inlet tube, a thermometer, a stirrer, and a reflux condenser was charged with 78 parts of stearamidoethyl acrylate, 6 parts of dimethylaminoethyl methacrylate (DM), 16 parts of hydroxybutyl acrylate (HBA), and 100 parts of methyl ethyl ketone (MEK). After replacing the atmosphere with nitrogen, 0.9 parts of t-butyl peroxypivalate was added and the mixture was reacted at 65°C for 12 hours to obtain a copolymer-containing solution of the polymer. As a post-treatment, 142 g of 0.4% acetic acid aqueous solution was added to 50 g of the obtained copolymer solution and dispersed. After heating using an evaporator, MEK was distilled off under reduced pressure to obtain a light brown copolymer aqueous dispersion (volatile organic solvent content: 1 wt% or less). Purified water was then added to prepare an aqueous dispersion with a solids concentration of 20 wt%. The ionic charge density of the aqueous dispersion was 350 μeq / g.

[0100] Example 1 To a pulp having a freeness of 550 cc (Canadian freeness), 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 0.3 g 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 stirred for 1 minute. Next, 3.5 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.

[0101] The pulp slurry was placed in a metal tank. A metal pulp molding die 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 molding die and mesh-like body from the side opposite the mesh-like body of the pulp molding die, 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 resistance and high-temperature water resistance, were evaluated, and the results are shown in Table 1.

[0102] <Example 2> Except for not adding alkyl ketene dimer (AKD), the experiment was carried out in the same manner as in Example 1. 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.

[0103] Example 3 Except for using the aqueous dispersion of Synthesis Example 2, the experiment was carried out in the same manner as in Example 1. 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.

[0104] Example 4 The experiment was carried out in the same manner as in Example 3, except that 2 g of the aqueous dispersion from Synthesis Example 2 diluted with water to a solids content of 10% was added, and 1.0 g of amphoteric PAM 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.

[0105] <Example 5> Except for not adding alkyl ketene dimer (AKD), the experiment was carried out in the same manner as in Example 3. 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.

[0106] Example 6 Except for not adding alkyl ketene dimer (AKD), the experiment was carried out in the same manner as in Example 4. 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.

[0107] Example 7 Except for using the aqueous dispersion of Synthesis Example 3, the experiment was carried out in the same manner as in Example 1. 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.

[0108] Example 8 An experiment was carried out in the same manner as in Example 3, except that the aqueous dispersion of Synthesis Example 4 was used. 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.

[0109] Example 9 Except for not adding alkyl ketene dimer (AKD), the experiment was carried out in the same manner as in Example 8. 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.

[0110] <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 used. 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.

[0111] <Comparative Example 2> Except for using the aqueous dispersion of Comparative Synthesis Example 2, the experiment was carried out in the same manner as in Example 1. 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.

[0112] [Table 1] [Industrial Applicability]

[0113] The polymers and greaseproofing compositions of the present disclosure are applicable to paper, particularly food containers and packaging.

Claims

1. An oil-proofing composition for paper, comprising a hydrocarbon group-containing polymer having repeating units formed from a monomer (a) in an amount of 80% by weight or more based on the polymer, Monomer (a) formula: R １２ -C(=O)-NH-R １３ -O-R １１ [In the formula, R １１ is -C(=O)CR １４ =CH ２ (R １４ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R １２ is a hydrocarbon group having 7 to 40 carbon atoms, R １３ is a hydrocarbon group having 1 to 5 carbon atoms. is an amide group-containing monomer represented by An oil-proofing composition for paper, wherein a hydrocarbon group-containing polymer contains a structure derived from a polymerization initiator.

2. The hydrocarbon group-containing polymer is (b) Repeating units formed from acrylic monomers having hydrophilic groups The oil-proofing composition for paper according to claim 1, which comprises:

3. 3. The oil-proofing composition for paper according to claim 2, wherein the monomer (b) is an acrylic monomer having a hydrophilic group which is an oxyalkylene group.

4. The hydrocarbon group-containing polymer is A repeating unit formed by a monomer (c) other than the monomers (a) and (b) that has an ethylenic carbon-carbon double bond and an anion-donating group or a cation-donating group The oil-proofing composition for paper according to claim 2, further comprising:

5. 2. The oil-proofing composition for paper according to claim 1, wherein the hydrocarbon group-containing polymer has a softening point of 80° C. or higher.

6. 2. The oil-proofing composition for paper according to claim 1, wherein the hydrocarbon group-containing polymer is obtained by emulsion polymerization.

7. 2. The oil-proofing composition for paper according to claim 1, further comprising at least one emulsifier selected from the group consisting of cationic emulsifiers, nonionic emulsifiers and anionic emulsifiers.

8. A hydrocarbon group-containing polymer is optionally A repeating unit formed by a monomer (c) other than the monomers (a) and (b) that has an ethylenic carbon-carbon double bond and an anion-donating group or a cation-donating group and 3. The oil-proofing composition for paper according to claim 2, wherein the amount of repeating units formed by the acrylic monomer (a) having a hydrocarbon group is 80 to 99% by weight, the amount of repeating units formed by the acrylic monomer (b) having a hydrophilic group is 1 to 15% by weight, and the amount of repeating units formed by the monomer (c) having an anion-donor group or a cation-donor group is 0 to 20% by weight, based on the polymer.

9. 2. The oil-proofing composition for paper according to claim 1, further comprising a liquid medium which is water or a mixture of water and an organic solvent.

10. 2. The oil-proofing composition for paper according to claim 1, which is used for paper internal addition.

11. 11. Grease-resistant paper, comprising the hydrocarbon group-containing polymer in the oil-proofing composition for paper according to any one of claims 1 to 10, adhered to the paper.

12. 12. The greaseproof paper according to claim 11, which is a pulp-molded product.

13. The greaseproof paper according to claim 11, which is a food packaging material or a food container.

14. A method for producing paper, comprising externally or internally treating paper with the oil-proofing composition for paper according to any one of claims 1 to 9.

15. A method for producing a pulp mold, comprising filling a mold with the oil-proofing composition for paper according to any one of claims 1 to 10 and a pulp slurry, and allowing water to permeate out of the mold to form pulp.

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