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-proofing agent composition and paper treated with the oil-proofing agent composition. Prior Art

[0002] Food packaging and food containers made of paper are required to prevent moisture and oil from seeping out of the food. Therefore, oil-proofing agents are applied internally or externally to the paper.

[0003] Patent document 1 (Japanese publication WO2020 / 054856) discloses an oil-resistant agent for paper containing a non-fluorinated copolymer. The non-fluorinated copolymer has: (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 (Japanese WO2020 / 241709 publication) discloses the use of non-fluorinated polymers and inorganic or organic particles to impart high-temperature oil resistance. Patent document 3 (Japanese Patent Application Publication No. 2018-16902) discloses a water-repellent agent for paper, which contains: a polymer containing a vinyl monomer having a long-chain alkyl group with 14 or more carbon atoms as a polymer component. [Prior Art Literature] [Patent Document]

[0004] [Patent Document 1] Japanese Patent Publication WO2020 / 054856 [Patent Document 2] Japanese Patent Publication WO2020 / 241709 [Patent Document 3] Japanese Patent Application Laid-Open No. 2018-16902 Summary of the Invention

[0005] [Problems to be solved by the invention] The present disclosure aims to provide an oil-proofing agent composition (oil-proofing agent) that can impart excellent oil resistance and, if necessary, excellent water resistance to paper. [Technical means to solve the problem]

[0006] The oil-resistant composition disclosed herein contains a hydrocarbon-containing polymer (ie, a non-fluorinated polymer). The hydrocarbon group-containing polymer preferably comprises 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 relative to the polymer. In the hydrocarbon group-containing polymer, preferably, an NH group-containing group exists between the polymer backbone and the hydrocarbon group having 1 to 40 carbon atoms. The hydrocarbon group-containing polymer is preferably a polyolefin, polyacrylic acid, 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. The so-called "softening point" refers to the temperature at which the complex viscosity of a polymer measured by dynamic mechanical analysis (DMA) reaches 1.0×104.

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

[0009] The preferred aspects of the invention are described below. Pattern 1: An oil-resistant agent composition contains a hydrocarbon-containing polymer, wherein the hydrocarbon-containing polymer has repeating units formed by monomers 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. Pattern 2: The oil-resistant agent composition as described in Example 1, wherein the hydrocarbon-containing polymer is a polyolefin, polyacrylic acid, polyester, polyamide, polycarbonate or polyurethane having an NH-containing group between the polymer main chain and the hydrocarbon group. Pattern 3: The oil-resistant agent composition as described in form 1 or 2, wherein the hydrocarbon-containing polymer has: a repeating unit formed by an ethylenic carbon-carbon double bond monomer having an NH-containing group between the polymer main chain and the hydrocarbon group. Pattern 4: The oil resistant agent composition as described in any one of aspects 1 to 3, wherein the hydrocarbon-containing polymer has: (a) a repeating unit formed from an acrylic monomer having a hydrocarbon group having 1 to 40 carbon atoms and a group containing an NH group, and (b) Repeating units formed from acrylic monomers having a hydrophilic group. Pattern 5: The oil resistant agent composition as described in aspect 4, wherein the hydrocarbon-containing polymer further has: A repeating unit formed from a monomer (c) having an ethylenic carbon-carbon double bond and an anion-donating group or a cation-donating group other than the monomers (a) and (b). Pattern 6: The oil resistant agent composition as described in any one of aspects 1 to 5, wherein the softening point of the hydrocarbon-containing polymer is above 80°C. Pattern 7: The oil resistant agent composition as described in any one of aspects 1 to 6, wherein the hydrocarbon-containing polymer is obtained by emulsion polymerization. Pattern 8: The oil-resistant agent composition as described in any one of aspects 1 to 7 further contains at least one emulsifier selected from cationic emulsifiers, nonionic emulsifiers and anionic emulsifiers. Pattern 9: The oil-resistant agent composition as described in 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 weight % relative to the polymer, the amount of repeating units formed by the acrylic monomer (b) having a hydrophilic group is 1 to 15 weight % relative to 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 weight % relative to the polymer. Pattern 10: The oil-resistant agent composition as described in any one of aspects 1 to 9 further contains water or a liquid medium that is a mixture of water and an organic solvent. Pattern 11: A greaseproof paper having a hydrocarbon-containing polymer in the greaseproofing agent composition as described in any one of aspects 1 to 10 attached thereto. Pattern 12: The oil-resistant paper as described in Example 11 is a pulp molded product. Pattern 13: The oil-resistant paper as described in embodiment 11 or 12 is a food packaging material or a food container. Pattern 14: A method for manufacturing paper comprises treating the paper with the oil-proofing agent composition described in any one of aspects 1 to 10 by external treatment or internal treatment. Pattern 15: The method for manufacturing paper as described in Example 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 for the pulp slurry is below 5000 ppm. Pattern 16: A method for manufacturing a pulp mold comprises: filling the oil-resistant agent composition described in any one of forms 1 to 10 and a pulp slurry into a mold, and allowing water to pass through the outside of the mold to form pulp. [Effects of the Invention]

[0010] According to the present disclosure, excellent oil and water resistance is imparted to paper. The paper exhibits excellent oil and water resistance even at high temperatures of 60°C to 110°C, such as 65°C to 100°C. Implementation Method

[0011] The hydrocarbon group-containing polymer has a hydrocarbon group with 1 to 40 carbon atoms and is selected from polyolefins, polyacrylic acids, polyesters, polyamides, polycarbonates, and polyurethanes. The hydrocarbon group-containing polymer is preferably a polymer having ethylenic carbon-carbon double bonds. The hydrocarbon group-containing polymer preferably has repeating units derived from a monomer having a hydrocarbon group having 1 to 40 carbon atoms. Preferably, an NH group-containing group exists 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, but preferably a monomer having an ethylenic carbon-carbon double bond, and particularly preferably an acrylic acid monomer. In the monomer having a hydrocarbon group having 1 to 40 carbon atoms, an NH-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-containing group include an amide group, a urethane group, a urea group, and a sulfonamide group.

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

[0014] Furthermore, the hydrocarbon group-containing polymer preferably has, in addition to the monomers (a) and (b), a repeating unit formed from (c) a monomer having an ion-donating group. The hydrocarbon group-containing polymer may also have, in addition to monomers (a), (b) and (c), 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 linear or branched hydrocarbon group having 1 to 40 carbon atoms. Since high oil resistance is achieved, the hydrocarbon group preferably has 10 to 40 carbon atoms, for example, 12 to 30 carbon atoms, and particularly preferably 15 to 30 carbon atoms. Alternatively, the hydrocarbon group may have 18 to 40 carbon atoms.

[0016] The acrylic monomer (a) having a hydrocarbon group is preferably a compound (an acrylate monomer or an acrylamide monomer) represented by the following formula: 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 -O- or -NH-, Y2 is a group containing an NH group, Z is a direct bond, 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 include a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, and a cyano group. X1 is preferably a hydrogen atom, a methyl group, or a chlorine atom. X1 is particularly preferably a hydrogen atom.

[0018] Y1 is -O- or -NH-, 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 straight chain structure or a branched structure. The number of carbon atoms in Z is preferably 2 to 4, particularly preferably 2. Specific examples of Z include a direct bond, -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2-, -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 divalent hydrocarbon group having 1 to 5 carbon atoms.

[0020] Y2 is an NH-containing group (spacer). Y2 forms a spacer site in the polymer that can form hydrogen bonds. This can be considered to improve oil resistance by forming hydrogen bonds with NH groups in the polymer. Y2 is preferably an amide group, a urethane group, a urea group, and a sulfonamide group. In other words, 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 is 1 or 2, preferably 1.

[0022] Preferred examples of acrylic acid monomers (a) having a divalent Z group and belonging to acrylate monomers are: 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. Particularly preferred is CH2=C(-X1)-C(=O)-O-(CH2)m-NH-C(=O)-R1. In the above formula, X1 and R1 have the same meanings as above, and m is 1 to 5.

[0023] Preferred specific examples of acrylic acid monomers (a) belonging to acrylate monomers having a trivalent Z group are: .

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

[0025] The acrylic monomer (a) having a hydrocarbon group is preferably an acrylic ester in which X1 is a hydrogen atom.

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

[0027] R11 represents an organic residue group having an ethylenically unsaturated polymerizable group. It is not particularly limited as long as it contains a double bond between carbon atoms. Specifically, examples include -C(=O)CR14=CH2, -CHR14=CH2, and -CH2CHR14=CH2. R14 can be a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. In addition to ethylenically unsaturated polymerizable groups, R11 can also have various organic groups, such as chain hydrocarbons, cyclic hydrocarbons, polyoxyalkylene groups, and polysiloxyalkylene groups. These organic groups may be substituted with 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 examples thereof include chain hydrocarbon groups and cyclic hydrocarbon groups. Chain hydrocarbon groups are preferred, and linear saturated hydrocarbon groups are particularly preferred. R12 has 1 to 40 carbon atoms, 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 may be straight-chain or branched, and may have an unsaturated bond, but is preferably straight-chain. The number of carbon atoms in R13 is preferably 2 to 4, particularly preferably 2. R13 is preferably an alkylene group.

[0030] The amide group-containing monomer may have one type of R12 (e.g., a compound in which only R12 has 17 carbon atoms), or a combination of multiple types of R12 (e.g., a mixture of a compound in which R12 has 17 carbon atoms and a compound in which R12 has 15 carbon atoms).

[0031] An example of an amide group-containing monomer is carboxamidoalkyl (meth)acrylate. Specific examples of the amido group-containing monomer include: palmitamide ethyl (meth)acrylate, stearamide ethyl (meth)acrylate, rocamidine ethyl (meth)acrylate, myristamide ethyl (meth)acrylate, lauramide ethyl (meth)acrylate, isostearyl ethyl (meth)acrylate, oleic acid ethyl (meth)acrylate, tert-butylcyclohexylhexanamide ethyl (meth)acrylate, adamantanecarboxylic acid ethyl (meth)acrylate, naphthamide ethyl (meth)acrylate, anthracenecarboxamide ethyl (meth)acrylate, palmitamide propyl (meth)acrylate, stearamide propyl (meth)acrylate, palmitamide ethyl vinyl ether, stearamide ethyl vinyl ether, palmitamide ethyl allyl ether, stearamide ethyl allyl ether, or mixtures thereof.

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

[0033] (b) Acrylic monomers with hydrophilic groups The hydrophilic acrylic monomer (b) is a monomer other than 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 hydrophilic acrylic monomer (b) is preferably a polyalkylene glycol mono(meth)acrylate and / or polyalkylene glycol di(meth)acrylate, or polyalkylene glycol mono(meth)acrylamide. The polyalkylene glycol mono(meth)acrylate, polyalkylene glycol di(meth)acrylate, or polyalkylene glycol mono(meth)acrylamide is 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 are independently a hydrogen atom or a methyl group, X3 are each independently a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, R is an alkylene group with 2 to 6 carbon atoms, n is an integer from 1 to 90. n is, for example, 1 to 50, especially 1 to 30, and particularly 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, a group represented by the formula -(CH2)x- or -(CH2)x1-(CH(CH3))x2- [wherein x1 and x2 are 0 to 6, for example, 2 to 5, and the total of x1 and x2 is 1 to 6; the order of -(CH2)x1- and -(CH(CH3))x2- is not limited to the described formula and can be random]. In -(RO)n-, R represents two or more types (for example, two to four types, especially two types). -(RO)n- can be, for example, a combination of -(R1O)n1- and -(R2O)n2- [wherein R1 and R2 are each different from each other and are alkylene groups having 2 to 6 carbon atoms, n1 and n2 are 1 or more, and the total of n1 and n2 is 2 to 90].

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

[0035] Specific examples of the acrylic monomer (b) having a hydrophilic group include the following, but are not limited thereto. 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)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. Particularly preferred are hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or hydroxyethylacrylamide.

[0044] (c) Monomers with ion-donating groups The monomer (c) having an ion-donating group is a monomer other than monomer (a) and monomer (b). Monomer (c) preferably has 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 monomers having an anion-donating group include monomers having a carboxyl group, a sulfonic acid group, or a phosphoric acid group. Specific examples of monomers 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, phosphoric acid (meth)acrylate, vinylbenzenesulfonic acid, acrylamide tert-butylsulfonic acid, or salts thereof.

[0046] Examples of the salt of the anion-donating group include alkali metal salts, alkaline earth metal salts, or ammonium salts, such as methylammonium salts, ethanolammonium salts, and triethanolammonium salts.

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

[0048] The cation-donating group of the salt is a salt with an acid (organic or inorganic). Preferred are 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). Preferred are dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and their salts.

[0049] Specific examples of the monomer having a cation donating group are shown below. CH2=CHCOO-CH2CH2-N(CH3)2 and its salts (such as acetate) CH2=CHCOO-CH2CH2-N(CH2CH3)2 and its salts (such as acetate) CH2=C(CH3)COO-CH2CH2-N(CH3)2 and its salts (such as acetate) CH2=C(CH3)COO-CH2CH2-N(CH2CH3)2 and its salts (such as acetate) CH2=CHC(O)N(H)-CH2CH2CH2-N(CH3)2 and its salts (such as acetate) CH2=CHCOO-CH2CH2-N(-CH3)(-CH2-C6H5) and its salts (such as acetate) CH2=C(CH3)COO-CH2CH2-N(-CH2CH3)(-CH2-C6H5) and its salts (such as 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] The monomer (c) having an ion-donating group is preferably methacrylic acid, acrylic acid, and dimethylaminoethyl methacrylate, and 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 such 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 ether, halogenated alkyl vinyl ether, alkyl ketone, butadiene, isoprene, chloroprene, glycidyl(meth)acrylate, aziridinium(meth)acrylate, benzyl(meth)acrylate, isocyanateethyl(meth)acrylate, cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, short-chain alkyl(meth)acrylate, maleic anhydride, (meth)acrylate having a polydimethylsiloxy group, and N-vinylcarbazole.

[0052] The amount of the repeating units formed from the monomer (a) (repeating units (a)) relative to the hydrocarbon group-containing polymer (or relative to the total of the repeating units (a) and the repeating units (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 the repeating unit formed from the monomer (a) (repeating unit (a)) relative to the hydrocarbon group-containing polymer (or relative to the total of the repeating unit (a) and the 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 the repeating unit formed from monomer (b) (repeating unit (b)) relative to the hydrocarbon group-containing polymer (or relative to the total of the repeating unit (a) and the repeating unit (b)) may be 0.5 to 15 weight %, 1 to 13 weight %, 3 to 12 weight %, 4 to 11 weight %, 5 to 10 weight %, 6 to 9 weight %, or 7 to 8 weight %. The amount of the repeating unit formed by monomer (c) relative to the hydrocarbon group-containing polymer may 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 the repeating unit formed from monomer (d) may be 1 to 10 wt%, 2 to 9 wt%, 3 to 8 wt%, 4 to 7 wt%, or 5 to 6 wt% relative to 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 and converted to polystyrene. In this specification, "(meth)acrylic acid" refers to acrylic acid or methacrylic acid. For example, "(meth)acrylate" refers to 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 hydrocarbon-containing polymers is not particularly limited, and various polymerization methods can be selected, including bulk polymerization, solution polymerization, emulsion polymerization, and radiation polymerization. For example, generally, solution polymerization in an organic solvent or emulsion polymerization using water or an organic solvent and water can be selected. After polymerization, the polymer is diluted with water and emulsified in water to prepare a treatment solution. In the present disclosure, after polymerization (e.g., solution polymerization or emulsion polymerization, preferably solution polymerization), it is preferred to add water and then perform desolvation to disperse the polymer in water. This allows the production of self-dispersible products without the need for an emulsifier. In the present disclosure, emulsion polymerization is preferably used. Compared with solution polymerization, emulsion polymerization can provide polymers with excellent high-temperature and oil resistance with the same monomer composition.

[0057] Examples of the organic solvent 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: N-methyl-2-pyrrolidone), dipropylene glycol, tripropylene glycol, and low molecular weight polyethylene glycol; and alcohols such as ethanol and isopropyl alcohol.

[0058] The polymerization initiator may be a peroxide, an azo compound, or a persulfate-based compound. Generally, the polymerization initiator is 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-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(t-butyl) peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, and t-butyl peroxypivalate.

[0059] In addition, preferred specific examples of water-soluble polymerization initiators 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, hydrogen peroxide, etc. The polymerization initiator is used in an amount of 0.01 to 5 parts by weight relative to 100 parts by weight of the monomer.

[0060] Furthermore, a chain transfer agent may be used for molecular weight adjustment. For example, a mercapto group-containing compound may be used. Specific examples include 2-mercaptoethanol, mercaptopropionic acid, and alkylmercaptan. The mercapto group-containing compound is used in an amount of 10 parts by weight or less, for example, 0.01 to 5 parts by weight, based on 100 parts by weight of the monomer.

[0061] Specifically, the hydrocarbon group-containing polymer can be produced by the following method. In solution polymerization, the monomers are dissolved in an organic solvent, the atmosphere is substituted with nitrogen, and then a polymerization initiator is added. The mixture is then heated and stirred at, for example, 40 to 120°C for 1 to 10 hours. The polymerization initiator is generally an oil-soluble polymerization initiator.

[0062] The organic solvent is inert to the monomers but can dissolve them, and includes: 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; hydrocarbon solvents such as n-heptane, n-hexane, n-octane, cyclohexane, methylcyclohexane, cyclopentane, methylcyclopentane, methylpentane, 2-ethylpentane, isoparaffinic hydrocarbons, liquid paraffin, decane, undecane, dodecane, mineral spirits, turpentine, and petroleum 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), and dipropylene glycol monomethyl ether (DPM). The organic solvent is used in an amount of 50 to 2000 parts by weight, for example, 50 to 1000 parts by weight, based on 100 parts by weight of the total monomers.

[0063] In the emulsion polymerization, a method is adopted in which the monomers are emulsified in water in the presence of an emulsifier, the atmosphere is substituted with nitrogen, a polymerization initiator is added, and the mixture is stirred at a temperature between 40°C and 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-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, or hydrogen peroxide; and Oil-soluble polymerization initiators, such as 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), benzyl peroxide, di(t-butyl) peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxytrimethylacetate, diisopropyl peroxydicarbonate, and t-butyl peroxytrimethylacetate, are used. The polymerization initiator is used in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the monomer.

[0064] To obtain a polymer aqueous dispersion with excellent shelf stability, it is preferred to use an emulsifying device, such as a high-pressure homogenizer or ultrasonic homogenizer, that imparts strong crushing energy to micronize the monomers in water, and then use an oil-soluble polymerization initiator to carry out polymerization. Furthermore, emulsifiers of various types, including anionic, cationic, and nonionic, can be used, with the amount used ranging from 0.5 to 20 parts by weight per 100 parts by weight of the monomers. Anionic and / or nonionic and / or cationic emulsifiers are preferred. If the monomers are not completely compatible, it is preferable to add a compatibilizer to fully compatibility these monomers, 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] 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, or isopentyl glycol. These can be used in an amount ranging from 1 to 50 parts by weight, for example, 10 to 40 parts by weight, relative to 100 parts by weight of water. The addition of NMP, DPM, 3-methoxy-3-methyl-1-butanol, or isopentyl glycol (preferably in an amount ranging from 1 to 20% by weight, particularly 3 to 10% by weight, relative to the composition) can improve the stability of the composition (especially the emulsion). Furthermore, examples of low-molecular-weight monomers include methyl methacrylate, glycidyl methacrylate, and 2,2,2-trifluoroethyl methacrylate. These can be used in an amount ranging from 1 to 50 parts by weight, for example, 10 to 40 parts by weight, relative to 100 parts by weight of the total monomer amount.

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

[0067] The ionic charge density of the oil-resistant agent composition may be -5000 μeq / g or higher, -2500 μeq / g or higher, -1500 μeq / g or higher, -500 μeq / g or higher, 0 μeq / g or higher, 100 μeq / g or higher, or 200 μeq / g or higher, preferably -2500 μeq / g or higher, more preferably -400 μeq / g or higher, for example, 0 μeq / g or higher. The ionic charge density of the oil-resistant agent composition may be 7500 μeq / g or lower, 5000 μeq / g or lower, 2500 μeq / g or lower, 1000 μeq / g or lower, 500 μeq / g or lower, 350 μeq / g or lower, 300 μeq / g or lower, or 250 μeq / g or lower, preferably 5000 μeq / g or lower, more preferably 800 μeq / g or lower, for example, 300 μeq / g or lower. In particular, the ionic charge density of the oil-proofing 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-proofing agent composition can be measured, for example, by the following method. <Measurement of ionic charge density> The anion demand of a 0.1 g / L aqueous solution of the sample was measured using a particle charge analyzer (MUTEK PCD-04 manufactured by BTG) using a 1 / 1000 equivalent potassium polyvinylsulfonate solution, and the ionic charge density (cationic charge density) was calculated using the following formula (1). Alternatively, a polydiallyldimethylammonium chloride solution was used instead of potassium polyvinylsulfonate, and the cation demand was similarly measured, and the ionic charge density (anionic charge density) was calculated using the following formula (1). [Number 1] Ionic charge density (μeq / g) = A / B (1) A: Cation demand or anion demand (μeq / L) B: Sample solution concentration (g / L)

[0068] The organic solvent in the polymer solution can be removed by heating (preferably under reduced pressure) the polymer solution (for example, at a temperature above 30° C., for example, at 50 to 120° C.).

[0069] The oil-proofing agent composition can be used to treat paper substrates (eg, surface treatment, internal treatment). The oil-resistant agent composition can be applied to the substrate by conventional methods. Typically, the composition is dispersed in an organic solvent or water for dilution, then applied to the substrate by known methods such as dip coating, spray coating, or bubble coating, followed by drying (surface treatment). Alternatively, the composition is added to a pulp slurry and then dehydrated, formed, and dried by known methods (internal application treatment). Examples of the paper substrate to be processed include paper, containers formed from paper, and molded articles formed from paper (e.g., pulp molds). The hydrocarbon-containing polymers disclosed herein adhere well to paper substrates.

[0070] Paper can be manufactured using conventional papermaking methods. The oil-resistant agent composition can be added to the pulp slurry before papermaking, or applied to the paper after papermaking. The oil-resistant agent composition treatment method disclosed herein is preferably an internal addition method.

[0071] The sizing of the additional treatment method can also be distinguished by the different coating methods as follows. One coating method involves supplying the coating liquid (glue) to a nip formed by passing the paper between two rubber rollers to create a reservoir called a pool. The paper is then passed through this reservoir, coating both sides of the paper with glue. This is known as pool-type twin-roll sizing. Other coating methods include gate roller sizing, which uses a surface transfer die to apply the glue, and rod metering size press sizing. With pool-type twin-roll sizing, the glue easily penetrates the interior of the paper, while with surface transfer sizing, the glue components tend to remain on the surface. Compared to pool-type twin-roll sizing, the coating layer tends to remain on the paper's surface, forming a more oil-resistant layer on the surface. In the present disclosure, even when the former pool-type double-roll sizing is used, oil resistance can be imparted to paper. The paper thus treated is briefly dried at room temperature or elevated temperature and then optionally heat treated at a temperature up to 300°C, for example, up to 200°C, and particularly within a temperature range of 80°C to 180°C, depending on the nature of the paper, thereby exhibiting excellent oil and water resistance.

[0072] This disclosure can be used on: gypsum board base paper, coated base paper, medium-quality paper, general lining materials and corrugated core paper, neutral pure white roll paper, neutral lining materials, rust-proof lining materials, metal-laminated paper, kraft paper, etc. In addition, it can also be used on: neutral printing note 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 may include any of the following: bleached or unbleached chemical pulps such as kraft pulp or sulfite pulp; high-yield pulps such as wood pulp, mechanical pulp, or thermomechanical pulp; and waste paper pulps such as old newspapers, old magazine paper, corrugated cardboard, and deinked paper. Furthermore, mixtures of the above pulp raw materials with synthetic fibers such as asbestos, polyamides, polyimides, polyesters, polyolefins, and polyvinyl alcohol may also be used.

[0074] Sizing agents may 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 can be 0.01 to 5% by weight relative to the paper pulp.

[0075] In the paper, commonly used papermaking chemicals may include, as needed, paper strengthening agents such as starch, modified starch, carboxymethyl cellulose, and polyamide polyamine-epichlorohydrin resins, coagulants, fixatives, retention aids, dyes, fluorescent dyes, slime control agents, and defoaming agents, among other additives used in paper production. Starch and modified starch are preferred. Starch, polyvinyl alcohol, dyes, coatings, anti-slip agents, etc. may also be used as needed, and the oil-proofing agent composition may be applied to paper by sizing, gate roll coating, bill-blade coating, calendaring, etc.

[0076] In the external application, the amount of the hydrocarbon-containing polymer in the oil-resistant layer is preferably 0.01 to 2.0 g / m², particularly preferably 0.1 to 1.0 g / m². The oil-resistant layer is preferably formed from the oil-resistant composition and starch and / or modified starch. The solid content of the oil-resistant composition for paper in the oil-resistant layer is preferably 2 g / m² or less. In the internal addition, the oil resistant agent composition is preferably mixed with the paper 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, and particularly 0.2 to 5.0 parts by weight, relative to 100 parts by weight of the paper pulp. In the external addition and internal addition, the weight ratio of starch and modified starch to hydrocarbon-containing polymer can be 10:90 to 98:2.

[0077] In the external application, even if a so-called pool-type two-roll sizing treatment is used, in which the treatment liquid is stored between the rolls and the base paper is passed through the treatment liquid between the rolls at an arbitrary roll speed and nip pressure, oil resistance can be imparted to the paper.

[0078] The hydrocarbon-containing polymer can be nonionic, cationic, anionic, or amphoteric. During the external treatment, the paper substrate may contain additives such as sizing agents, paper strengthening agents, coagulants, retention aids, or coagulants. These additives can be nonionic, cationic, anionic, or amphoteric. The ionic charge density of the additives can be between -10,000 and 10,000 μeq / g, preferably between -4,000 and 8,000 μeq / g, and more preferably between -1,000 and 7,000 μeq / g. The amount of additives (solid content or active ingredient) such as sizing agents, paper strengthening agents, coagulants, retention aids, or coagulants relative to the paper pulp is generally 0.1 to 10% by weight (e.g., 0.2 to 5.0% by weight). For paper substrates containing cationic additives (e.g., sizing agents, paper strengthening agents, coagulants, retention aids, or coagulants), the oil-resistant agent composition is preferably anionic.

[0079] In the internal addition process, papermaking is preferably performed using 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 strengthening agents, coagulants, retention aids, or coagulants) and a hydrocarbon-containing polymer may be added to the pulp slurry. Since paper pulp is generally anionic, at least one of the additive and the hydrocarbon-containing polymer is preferably cationic or amphoteric in order to ensure good adhesion of the additive and the hydrocarbon-containing polymer to the paper. Preferred combinations include: a cationic or amphoteric additive and an anionic hydrocarbon-containing polymer; a combination of an anionic additive and a cationic or amphoteric hydrocarbon-containing polymer; and a combination of a cationic or amphoteric additive and a hydrocarbon-containing polymer. It is more preferred to set the ionic charge density of additives such as sizing agents, paper strengthening agents, coagulants, retention aids or coagulants to -1000 to 7000 μeq / g for papermaking, and it is even more preferred to set the ionic charge density to 100 to 1000 μeq / g (for example, 330 μeq / g, 420 μeq / g or 680 μeq / g) for papermaking.

[0080] Examples of additives (such as sizing agents, paper strengthening agents, coagulants, retention aids, or coagulants) include: alkyl ketene dimer (AKD), alkenyl succinic anhydride (ASA), styrene-based polymers (styrene / maleic acid polymers, styrene / acrylic acid polymers), urea-formaldehyde polymers, polyethyleneimine, melamine-formaldehyde polymers, polyamide-epichlorohydrin polymers, polyacrylamide polymers, polyamine polymers, polydiallyldimethylammonium chloride, alkylamine-epichlorohydrin condensates, condensates of ethylene dichloride and polyalkylene polyamines, dicyandiamide-formaldehyde condensates, dimethyldiallylammonium chloride polymers, and olefin / maleic anhydride polymers. Examples of the polyacrylamide polymer include nonionic polyacrylamide polymers, anionic polyacrylamide polymers, and amphoteric polyacrylamide polymers.

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

[0082] When the oil-resistant agent composition is used as an internal treatment agent, it can be added to a resin, such as a thermoplastic resin, to impart oil resistance to the resin. The oil-resistant agent composition can be used when manufacturing resin molded articles. The polymer is obtained by removing the liquid medium, or the liquid medium and emulsifier, from a liquid (solution or dispersion) containing the polymer. For example, the polymer can be obtained by reprecipitating 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 produced by a production method comprising the following steps: a step of mixing a resin and a polymer to obtain a resin composition, and a step of molding the resin composition. Preferably, the molded article is produced by melt-kneading using an extruder or the like. Generally speaking, thermoplastic resins and polymers are compatible in a molten state. Kneading can be performed using conventional methods, such as a single-screw extruder, a twin-screw extruder, or rollers. The resulting resin composition is then formed by extrusion, injection molding, compression molding, blow molding, or molding. The resin composition is formed into molded articles of various shapes. After forming, the resulting molded articles can be further heated in an oven, drying furnace, or the like. The molded articles can be single-layer or have multiple layers, such as 2 to 10 layers, for example 3 to 5 layers.

[0084] The substrate may be paper, especially pulp moulding. Pulp molds can be made by filling a mold with pulp slurry containing an oil-resistant composition and allowing water to penetrate the mold to form the pulp. Alternatively, injection molding can be used as the molding method. Pulp molds can be manufactured by filling the cavity of a water-permeable mold for pulp molds with papermaking liquid and allowing the water to penetrate the mold to form the mold. Methods for allowing the water in the pulp slurry to penetrate the mold include allowing the water to penetrate naturally under normal pressure and forcing the water to penetrate by reducing the pressure outside the mold. In injection molding, a molding material containing pulp, starch, water, and an oil-resistant agent is injection-molded to produce a three-dimensional structure (pulp mold).

[0085] The conductivity of the pulp slurry (to which the oil-resistant agent composition has been added) 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. Within these ranges, high oil resistance is achieved. The conductivity can be measured using, for example, the LAQUAtwin AS-EC-33 manufactured by AS ONE. 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 is obtained. The hardness of the water used for the pulp slurry is preferably 5000 ppm or less, more preferably 3000 ppm or less, even more preferably 1000 ppm or less, and particularly preferably 500 ppm or less. Within this range, high oil resistance can be achieved.

[0086] Molded articles can be used in applications where thermoplastic resins are used, particularly those that exhibit excellent dirt removability and damage resistance. Applications for these molded articles include: automobiles (exterior and interior parts) (e.g., bumpers, instrument panels, door trims), home appliances (e.g., washing machines and refrigerators) (e.g., housings, refrigerator inner doors, trays, and fruit and vegetable compartment containers), various housings, buildings (interiors and parts) (e.g., handrails, wallpaper, tables, chairs, toilet seats and lids, bathtubs), electronic equipment (e.g., smartphone housings), drains, pipelines, tableware, flooring, gasoline tanks, fuel pipes, and office automation equipment. Among these applications, automotive interior parts, home appliance interior parts, and buildings are particularly preferred. Preferably, the oil resistant agent composition is added to the thermoplastic resin and the oil resistant agent composition and the thermoplastic resin are mixed (internal addition treatment).

[0087] In this disclosure, the article being treated is treated with an oil-resistant composition. "Treatment" refers to applying the oil-resistant composition to the article being treated by impregnation, spraying, coating, mixing, or addition. The treatment allows the hydrocarbon-containing polymer, an active ingredient in the oil-resistant composition, to penetrate the interior of the article being treated and / or adhere to its surface. The hydrocarbon-containing polymer adheres to the interior and / or surface of the article being treated. When the treated object is, for example, pulp slurry or thermoplastic resin, the hydrocarbon-containing polymer, which is an effective component of the oil-proofing agent composition, is attached to the interior and / or surface of the treated object by the treatment. [Example]

[0088] Next, the present disclosure is specifically described with reference to examples, comparative examples, and test examples, but these descriptions are not intended to limit the present disclosure. In the following description, parts, percentages, or ratios represent parts by weight, percentages by weight, or ratios by weight unless otherwise specified.

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

[0090] [Softening point] The softening point of the polymer was determined by dynamic viscoelasticity measurement (DMA). The polymer aqueous dispersion was dried in an oven at approximately 130°C for 30 minutes to obtain a sample copolymer for measurement. In the case of an emulsified polymer, 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 from the emulsifier, obtaining the sample copolymer for measurement. The complex viscosity (η*) of the polymer was measured using a dynamic viscoelasticity measuring apparatus, RHEOSOL-G3000 (manufactured by UBM Co., Ltd.), at a heating rate of 1°C / min. The softening point was defined as the temperature at which the complex viscosity reached 1.0 × 10⁴.

[0091] [High temperature oil resistance] Pour 100ml of the evaluation liquid (corn oil) at 65°C or 80°C into a container-shaped pulp molded article. After standing for 30 minutes, discard the evaluation liquid and visually evaluate the degree of liquid penetration into the pulp molded article (container) according to the following criteria. 4: Almost no oil leakage was observed on the inner side of the bottom of the container 3: No oil leakage was observed on the outside of the bottom of the container 2: Oil leakage is observed on less than 5% of the outer area of ​​the bottom of the container 1: Oil leakage is observed on more than 5% and less than 50% of the outer area of ​​the bottom of the container 0: Oil leakage is observed on more than 50% of the outer area of ​​the container bottom

[0092] [High temperature water resistance] Pour 100ml of the evaluation liquid (water) at 100°C into a container-shaped pulp molded article. After standing for 30 minutes, discard the evaluation liquid and visually evaluate the degree of penetration of the evaluation liquid into the pulp molded article (container) according to the following criteria. 4: Almost no leakage was observed on the inner side of the container bottom 3: No leakage was observed on the outside of the bottom of the container 2: Liquid seepage is observed on less than 5% of the outer area of ​​the container bottom 1: Liquid seepage is observed on more than 5% and less than 50% of the outer area of ​​the container bottom 0: Liquid seepage is observed on more than 50% of the outer area of ​​the container bottom

[0093] <Synthesis example 1> 90 parts of stearamidoethyl acrylate, 3 parts of dimethylaminoethyl methacrylate (DM), 7 parts of hydroxybutyl acrylate (HBA), 370 parts of pure water, 1.1 parts of acetic acid, and 10 parts of alkylbis(2-hydroxyalkyl)methylammonium chloride were placed in a 1L plastic container. The mixture was heated to 80°C and stirred at 2000 rpm for 1 minute using a homomixer. The mixture was then ultrasonically emulsified and dispersed for 15 minutes. The emulsified dispersion was transferred to a 1000cc four-necked flask equipped with a nitrogen inlet, thermometer, stirring rod, and reflux tube. After nitrogen purging, 1 part of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added and the reaction was continued at 60°C for 4 hours to obtain an aqueous dispersion of the polymer. Purified 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 250 μeq / g.

[0094] 〈Synthesis example 2〉 90 parts of stearamidoethyl acrylate, 3 parts of dimethylaminoethyl methacrylate (DM), 7 parts of hydroxybutyl acrylate (HBA), 290 parts of pure water, 0.8 parts of acetic acid, 7 parts of alkylbis(2-hydroxyalkyl)methylammonium chloride, and 3 parts of polyoxyethylene alkyl ether were placed in a 1L plastic container. The mixture was heated to 80°C and stirred at 2000 rpm for 1 minute using a homomixer. The mixture was then ultrasonically emulsified and dispersed for 15 minutes. The emulsified dispersion was transferred to a 1000cc four-necked flask equipped with a nitrogen inlet, thermometer, stirring rod, and reflux tube. After nitrogen purging, 1 part of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added, and the reaction was allowed to proceed at 60°C for 4 hours to obtain an aqueous dispersion of the polymer. Purified water was then 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 stearamidoethyl acrylate, 3 parts of dimethylaminoethyl methacrylate (DM), 7 parts of hydroxybutyl acrylate (HBA), and 100 parts of methyl ethyl ketone (MEK) were placed in a 500 ml four-necked flask equipped with a nitrogen inlet tube, a thermometer, a stirring rod, and a reflux tube. After nitrogen substitution, 0.9 parts of t-butyl peroxytrimethylacetate was added, and the reaction was carried out at 65°C for 12 hours to obtain a polymer-containing copolymer solution. As a post-treatment, 71 g of a 0.4% aqueous acetic acid solution was added to 50 g of the resulting copolymer solution for dispersion. MEK was then distilled off using an evaporator under heating and reduced pressure to obtain a light brown aqueous copolymer dispersion (volatile organic solvent content was less than 1% by weight). Purified 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 stearamidoethyl acrylate, 3 parts of dimethylaminoethyl methacrylate (DM), 7 parts of hydroxybutyl acrylate (HBA), 290 parts of pure water, 0.8 parts of acetic acid, 7 parts of alkyldimethylbenzylammonium chloride, and 10 parts of polyoxyethylene alkyl ether were placed in a 1L plastic container. The mixture was heated to 80°C and stirred at 2000 rpm for 1 minute using a homomixer. The mixture was then ultrasonically emulsified and dispersed for 15 minutes. The emulsified dispersion was transferred to a 1000cc four-necked flask equipped with a nitrogen inlet, thermometer, stirring rod, and reflux tube. After nitrogen purging, 1 part of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added, and the reaction was continued at 60°C for 4 hours to obtain an aqueous dispersion of the polymer. Purified water was then 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 stearamidoethyl acrylate, 6 parts of dimethylaminoethyl methacrylate (DM), 16 parts of hydroxybutyl acrylate (HBA), 370 parts of pure water, 2.2 parts of acetic acid, and 10 parts of alkylbis(2-hydroxyalkyl)methylammonium chloride were placed in a 1L plastic container. The mixture was heated to 80°C and stirred at 2000 rpm for 1 minute using a homomixer. The mixture was then ultrasonically emulsified and dispersed for 15 minutes. The emulsified dispersion was transferred to a 1000cc four-necked flask equipped with a nitrogen inlet, thermometer, stirring rod, and reflux tube. After nitrogen purging, 1 part of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added and the reaction was continued at 60°C for 4 hours to obtain an aqueous dispersion of the polymer. Purified 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 370 μeq / g.

[0098] <Comparative Synthesis Example 2> 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) were placed in a 500 ml four-necked flask equipped with a nitrogen inlet tube, a thermometer, a stirring rod, and a reflux tube. After nitrogen substitution, 0.9 parts of t-butyl peroxytrimethylacetate was added, and the reaction was carried out at 65°C for 12 hours to obtain a polymer-containing copolymer solution. As a post-treatment, 142 g of a 0.4% aqueous acetic acid solution was added to 50 g of the resulting copolymer solution for dispersion. MEK was then distilled off using an evaporator under heating and reduced pressure to obtain a light brown aqueous copolymer dispersion (volatile organic solvent content was less than 1% by weight). Purified 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, 2000 g of a 0.5 wt% aqueous dispersion of a mixture of 70 parts of bleached broadleaf kraft pulp and 30 parts of bleached coniferous kraft pulp, beaten to a filterability of 550 cc (Canadian Freeness), was added. Subsequently, 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 stirring was continued for 1 minute. Then, 3.5 g of the aqueous dispersion of Synthesis Example 1, diluted with water to a solid content of 10%, was added, and stirring was continued for 1 minute.

[0100] The pulp slurry is placed in a metal tank. A metal pulp mold with numerous suction holes is located at the bottom of the tank, with a mesh positioned above it. A vacuum pump is used to extract and dehydrate the aqueous pulp-containing composition from the side of the mold opposite the mesh, through the mold and the mesh. This allows the solids (pulp, etc.) contained in the aqueous pulp-containing composition to accumulate on the mesh, resulting in an intermediate pulp mold. The intermediate pulp mold is then pressurized and dried from above and below by metal male and female molds heated to 60 to 200°C. This results in a pulp molded product shaped like a container. The ratio of each component relative to the pulp content in the resulting pulp molded product, as well as the results of evaluations of its high-temperature oil and water resistance, are shown in Table 1.

[0101] <Example 2> The experiment was conducted in the same manner as in Example 1, except that alkyl ketene dimer (AKD) was not added. Table 1 shows the ratio of each component relative to the pulp content in the resulting pulp molded article, as well as the results of evaluations of high-temperature oil resistance and high-temperature water resistance.

[0102] <Example 3> The experiment was conducted in the same manner as in Example 1, except that the aqueous dispersion of Synthesis Example 2 was used. Table 1 shows the ratio of each component relative to the pulp content in the resulting pulp molded article, as well as the results of evaluations of high-temperature oil resistance and high-temperature water resistance.

[0103] <Example 4> The experiment was conducted 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 10% solids content, and 1.0 g of amphoteric PAM, diluted with water to a 10% solids content, were added. Table 1 shows the ratio of each component relative to the pulp content in the resulting pulp molded articles, as well as the results of evaluations of high-temperature oil resistance and high-temperature water resistance.

[0104] <Example 5> The experiment was conducted in the same manner as in Example 3, except that alkyl ketene dimer (AKD) was not added. The ratio of each component in the resulting pulp molded article relative to the pulp content, as well as the results of evaluation of high-temperature oil resistance and high-temperature water resistance, are shown in Table 1.

[0105] <Example 6> The experiment was conducted in the same manner as in Example 4, except that alkyl ketene dimer (AKD) was not added. Table 1 shows the ratio of each component relative to the pulp content in the resulting pulp molded article, as well as the results of evaluation of high-temperature oil resistance and high-temperature water resistance.

[0106] <Example 7> The experiment was conducted in the same manner as in Example 1, except that the aqueous dispersion of Synthesis Example 3 was used. Table 1 shows the ratio of each component relative to the pulp content in the resulting pulp molded article, as well as the results of evaluations of high-temperature oil resistance and high-temperature water resistance.

[0107] <Example 8> The experiment was conducted in the same manner as in Example 3, except that the aqueous dispersion of Synthesis Example 4 was used. Table 1 shows the ratio of each component relative to the pulp content in the resulting pulp molded article, as well as the results of evaluations of high-temperature oil resistance and high-temperature water resistance.

[0108] <Example 9> The experiment was conducted in the same manner as in Example 8, except that alkyl ketene dimer (AKD) was not added. Table 1 shows the ratio of each component relative to the pulp content in the resulting pulp molded article, as well as the results of evaluations of high-temperature oil resistance and high-temperature water resistance.

[0109] <Comparative Example 1> The experiment was conducted in the same manner as in Example 1, except that the aqueous dispersion of Comparative Synthesis Example 1 was used. Table 1 shows the ratio of each component relative to the pulp content in the resulting pulp molded article, as well as the results of evaluations of high-temperature oil resistance and high-temperature water resistance.

[0110] <Comparative Example 2> The experiment was conducted in the same manner as in Example 1, except that the aqueous dispersion of Comparative Synthesis Example 2 was used. Table 1 shows the ratio of each component relative to the pulp content in the resulting pulp molded article, as well as the results of evaluations of high-temperature oil resistance and high-temperature water resistance.

[0111] [Table 1] [Industrial Applicability]

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

Claims

1. A paper oil-resistant agent composition comprising a hydrocarbon-containing polymer, wherein the hydrocarbon-containing polymer comprises repeating units (a) formed of a monomer having a hydrocarbon group having 7 to 40 carbon atoms and an NH group, in an amount of 80% by weight or more relative to the polymer, 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.

2. The paper oil-resistant agent composition as claimed in claim 1, wherein the hydrocarbon-containing polymer has: (b) repeating units formed by acrylic monomers having hydrophilic groups, and (c) repeating units formed by monomers having vinyl carbon-carbon double bonds and anionic or cationic donor groups other than monomers (a) and (b), which are optional components.

3. The paper oil-resistant agent composition as described in claim 2, wherein, Monomer (b) is an acrylic monomer with a hydrophilic alkyl group.

4. The paper oil-resistant agent composition as claimed in claim 2, wherein the hydrocarbon-containing polymer further comprises: repeating units formed by monomer (c).

5. The paper oil-resistant agent composition as described in claim 1, wherein the softening point of the hydrocarbon-based polymer is above 80°C.

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

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

8. The paper oil-resistant agent composition as claimed in claim 2, wherein the amount of repeating units formed by monomer (a) is 80 to 99% by weight relative to the polymer, the amount of repeating units formed by monomer (b) is 1 to 15% by weight relative to the polymer, and the amount of repeating units formed by monomer (c) is 0 to 20% by weight relative to the polymer.

9. The paper oil-resistant agent composition as described in claim 1, further comprising water or a liquid medium being a mixture of water and an organic solvent.

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

11. 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 10 attached to the paper.

12. The greaseproof paper as described in claim 11 is a pulp molded product.

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

14. A method of 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 10.

15. A method for manufacturing a pulp mold, comprising: filling a mold with an oil-resistant paper composition and pulp slurry as described in any one of claims 1 to 10, and allowing water to pass through the outside of the mold to form pulp.