Oil-resistant agent composition and oil-resistant product

Abstract

Provided is a fluorine-free oil-resistant agent composition which is capable of imparting excellent oil resistance to a base material without using a fluorine-based compound, and which is capable of obtaining an oil-resistant paper having both excellent oil resistance and air permeability, in particular when a paper base material is treated. A non-fluorine oil-resistant agent composition which contains a non-fluorine compound having a C1-60 hydrocarbon group and a neutralized acidic functional group in at least constituent units, and which is characterized in that: the ratio of the neutralized acidic functional group in the non-fluorine compound is 0.4-21 mass%; the non-fluorine compound is a copolymer containing structural units derived from an unsaturated monomer having a C1-60 hydrocarbon group, an unsaturated monomer having an acidic functional group, and an unsaturated monomer having a nonionic functional group. The unsaturated monomer having a nonionic functional group is an unsaturated monomer having a hydroxyl group as a nonionic functional group. The mass ratio of the unsaturated monomer having a hydroxyl group to the unsaturated monomer having an acidic functional group (unsaturated monomer having a hydroxyl group / unsaturated monomer having an acidic functional group) is 2.6 or less.

Description

Technical Field

[0001] The present invention relates to an oil-proofing agent composition and an oil-resistant product (especially oil-resistant paper) obtained by using the same. Background Art

[0002] In the past, research has been conducted to impart antifouling functions to substrates in various fields such as the fiber field and the paper field. Examples of antifouling functions include the prevention of adhesion (prevention of penetration) of aqueous dirt due to water repellency, the prevention of adhesion (prevention of penetration) of oily dirt due to oil repellency or oil resistance, and the removal of attached dirt due to washing, etc.

[0003] In the past, compounds with perfluoroalkyl groups were used because they can impart excellent water repellency, oil repellency, and oil resistance. However, in recent years, the toxicity and environmental residuality of perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) have been considered problems, and the use of agents containing them and agents that may decompose and generate them after being released into the environment has begun to be avoided. Furthermore, substitution with agents composed of non-fluorine compounds that do not use fluorine compounds themselves is underway.

[0004] Among the above-mentioned antifouling functions, oil repellency and oil resistance largely rely on the characteristics of perfluoroalkyl groups, and it is difficult to switch to non-fluorine-based agents.

[0005] As an example of oil-resistant products using such agents, oil-resistant paper is widely used as a raw material for packaging containers for detergents, snacks, dry foods, etc. There are various uses for it. Regarding the board paper with oil resistance, it is often used for boxes for foods such as snacks, especially boxes for chocolate snacks containing a large amount of fat components, and regarding the paper with oil resistance given to the thin paper, it is often used for containers for packaging fast food and other fried foods, packaging containers for take-out food in department stores, convenience stores, etc.

[0006] As a means of imparting oil resistance to paper, for example, cooking sheets having an oil-resistant layer formed by coating a fluorine-based oil-resistant agent on the surface of paper or board, or oil-resistant board for snack boxes having a fluorine-based oil-resistant agent layer formed between paper layers, etc., can be cited. However, when paper using a fluorine-based oil-resistant agent is heated at a food cooking temperature of 100 to 180°C, fluorotelomer alcohols and the like are confirmed to be generated, and there is a further demand for oil-resistant paper that does not use a fluorine-based oil-resistant agent.

[0007] As oil-resistant paper to replace fluorine-based oil-resistant agents, there are disclosed oil-resistant paper obtained by coating a non-fluorine-based acrylic resin oil-resistant agent on a paper substrate, polyethylene film laminated paper, oil-resistant paper coated with a polyethylene resin, oil-resistant paper using silicone-based or wax-based oil-resistant agents, and the manufacturing technology of the oil-resistant paper. However, since each has its own advantages and disadvantages, although some of them have been put into practical use, there is still a strong demand for improvement from users.

[0008] However, oil-resistant paper using a fluorine-based oil-resistant agent obtains oil resistance with a small amount of the agent used, and therefore mainly adopts a method of adding the agent into pulp slurry during the papermaking process or applying the agent to the surface by size press after papermaking.

[0009] On the other hand, when non-fluorine compounds are used, the oil repellency is insufficient compared with fluorine compounds, and a thick oil-resistant layer is usually provided on the surface of the paper to prevent the penetration of grease components, etc. For example, a method of obtaining an oil-resistant layer formed into a film without pinholes by coating a non-fluorine acrylic resin emulsion, a method of laminating a polyethylene film, etc. can be cited.

[0010] However, in order for the oil-resistant paper obtained by the above method to exhibit the same oil resistance as the fluorine-based oil-resistant agent, a large amount of oil-resistant agent must be used to form the oil-resistant layer, and this is accompanied by the problem that air permeability is not obtained at all or the air permeability is greatly reduced. When hot food is placed in a packaging material that does not have sufficient air permeability, or when it is reheated in a microwave oven, the generated water vapor is difficult to release to the outside, resulting in problems such as deterioration of the taste of foods such as potato chips, croquettes, and tempura that value the freshly made taste.

[0011] Here, for example, Patent Document 1 proposes an oil-resistant paper (Ogan-style air permeability of 10,000 seconds or less), which comprises a paper substrate and oil-resistant layers on both sides of the paper substrate, wherein the paper substrate contains hardwood bleached kraft pulp and conifer bleached kraft pulp as pulp, the pulp blending ratio is in the range of 0 / 100 to 70 / 30 (mass ratio), the beating degree based on the Schober-Rieger method is 45° SR or more, and the bulk density is 0.45 g / cm 3 Above and 0.75g / cm 3 The oil-resistant layer contains at least styrene-acrylic copolymer resin and paraffin wax as oil-resistant agents, and the mixing ratio of the styrene-acrylic copolymer resin and the paraffin wax is 90:10 to 10:90 (mass ratio).

[0012] In addition, for example, Patent Document 2 proposes an oil-resistant paper having an oil-resistant layer formed on at least one side of a paper support, wherein the oil-resistant layer contains starch and wax containing a hydrophobic base, and the oil-resistant paper has an Oken-type air permeability of less than 2000 seconds as measured in accordance with the provisions of JAPAN TAPPI Pulp Test Method No. 5-2:2000.

[0013] In addition, as an oil-proof agent capable of imparting oil resistance and water resistance to paper, for example, Patent Document 3 proposes an oil-proof agent for paper comprising a non-fluorinated copolymer having: a) a repeating unit formed from an acrylic monomer having a long-chain hydrocarbon group having 7 to 40 carbon atoms, and (b) a repeating unit formed from an acrylic monomer having a hydrophilic group.

[0014] In addition, for example, Patent Document 4 discloses oil-resistant paper obtained by using a non-fluorine-based material and a method for producing the same, and proposes using an acrylic copolymer obtained by emulsion polymerization of a monomer mixture of (a) a monomer containing an ethylenically unsaturated carboxylic acid: 5 to 80% by mass, (b) a (meth) alkyl acrylate monomer: 10 to 95% by mass, and (c) at least one monomer selected from other monomers copolymerizable with these monomers: 0 to 80% by mass as an oil-resistant agent.

[0015] However, the oil-resistant paper obtained by coating an oil-resistant agent disclosed in Patent Documents 1 to 4 has problems such as insufficient air permeability and deterioration of the texture of food, although oil resistance can be obtained.

[0016] In addition, regarding oil resistance, sufficient performance may not be exhibited due to the influence of the production method of the paper base material, etc.

[0017] Prior art literature Patent Literature Patent Document 1: Japanese Patent Application Publication No. 2020-122250 Patent Document 2: Japanese Patent Application Publication No. 2013-237941 Patent Document 3: International Publication No. 2020 / 054856 Patent Document 4: Japanese Patent Application Publication No. 2014-025163 Summary of the invention

[0018] Technical problem to be solved by the invention The main object of the present invention is to provide a non-fluorine-based oil-proofing agent composition that can impart excellent oil resistance to a substrate without using a fluorine-based compound, and in particular, when treating a paper substrate, can obtain an oil-resistant paper having both excellent oil resistance and air permeability.

[0019] Technical solutions for solving technical problems The inventors of the present invention have conducted intensive research to solve the above-mentioned problems, and have found that by including a non-fluorine-based compound having at least a hydrocarbon group having 1 to 60 carbon atoms and a neutralized acidic functional group in the structure, and controlling the proportion of the neutralized acidic functional group (excluding the mass of the neutralizer) within a specified range, it is possible to impart excellent oil resistance and excellent air permeability to paper even without including a fluorine-based compound. The present invention is the result of further intensive research based on such insights.

[0020] That is, the present invention provides an invention having the following configuration.

[0021] Item 1. A non-fluorine-based oil-proofing agent composition comprising a non-fluorine-based compound having at least a hydrocarbon group having 1 to 60 carbon atoms and a neutralized acidic functional group in a structural unit, and The neutralized acidic functional groups of the non-fluorine-containing compound account for 0.4 to 21% by mass. When the non-fluorine-based compound is a copolymer comprising structural units derived from an unsaturated monomer having a hydrocarbon group having 1 to 60 carbon atoms, an unsaturated monomer having an acidic functional group and an unsaturated monomer having a nonionic functional group, and the unsaturated monomer having a nonionic functional group is an unsaturated monomer having a hydroxyl group as a nonionic functional group, the mass ratio of the unsaturated monomer having a hydroxyl group to the unsaturated monomer having an acidic functional group (unsaturated monomer having a hydroxyl group / unsaturated monomer having an acidic functional group) is 2.6 or less.

[0022] Item 2. The non-fluorine-based oil repellent composition according to Item 1, wherein the non-fluorine-based compound comprises a structure derived from the unsaturated monomer having a hydrocarbon group having 1 to 60 carbon atoms and the unsaturated monomer having an acidic functional group.

[0023] Item 3. The non-fluorine-based oil resistant composition according to Item 1 or 2, wherein the non-fluorine-based compound further includes a structure derived from the unsaturated monomer having a nonionic functional group.

[0024] Item 4. The non-fluorine-based oil resistant composition according to any one of Items 1 to 3, wherein the nonionic functional group is at least one selected from a hydroxyl group, a phenolic hydroxyl group, a nitrile group, an amide group, a (thio)urethane group, a (thio)urea group, a (thio)carbonate group, and an ester group.

[0025] Item 5. The non-fluorine-based oil repellent composition according to any one of Items 1 to 4, which is used for paper.

[0026] Item 6. The non-fluorine-based oil repellent composition according to any one of Items 1 to 5, which is used for food contact applications.

[0027] Item 7. An oil-resistant product, wherein the non-fluorine compound according to any one of Items 1 to 6 is present on at least one of the surface and the interior of a substrate.

[0028] Item 8. A greaseproof paper comprising the non-fluorine compound described in any one of Items 1 to 6, The Kit value of the flat surface of the oil-proof paper measured according to TAPPI UM-557 is 1 to 6.

[0029] Item 9. The oil-resistant paper according to Item 8, wherein the oil-resistant paper has a Gurley air permeability of 1000 seconds or less as measured in accordance with JIS P 8117:2009.

[0030] Effects of the Invention By treating the substrate with the non-fluorine-based oil-resistant agent composition of the present invention, it is possible to impart excellent oil resistance to the substrate without using a fluorine-based compound. In particular, the oil-resistant paper obtained by treating paper with the non-fluorine-based oil-resistant agent composition of the present invention has not only excellent oil resistance (Kit method) but also excellent air permeability. Therefore, when the oil-resistant paper is manufactured using the non-fluorine-based oil-resistant agent composition of the present invention, it is possible to effectively suppress the deterioration of the taste of food.

[0031] In addition, the non-fluorine-based oil repellent composition of the present invention can easily adjust the hydrophilic-hydrophobic balance, and the water resistance can be adjusted according to requirements such as printing suitability. DETAILED DESCRIPTION

[0032] The non-fluorine-based oil resistant composition of the present invention is a non-fluorine-based oil resistant composition comprising a non-fluorine-based compound having at least a hydrocarbon group having 1 to 60 carbon atoms and a neutralized acidic functional group in the structure, and the ratio of the neutralized acidic functional group in the non-fluorine-based compound (excluding the mass of the neutralizer) is 0.4 to 21 mass %. In the non-fluorine-based oil resistant composition of the present invention, when the non-fluorine-based compound is a copolymer comprising structural units derived from an unsaturated monomer having a hydrocarbon group having 1 to 60 carbon atoms, an unsaturated monomer having an acidic functional group, and an unsaturated monomer having a nonionic functional group, and when the unsaturated monomer having a nonionic functional group is an unsaturated monomer having a hydroxyl group as a nonionic functional group, the mass ratio of the unsaturated monomer having a hydroxyl group to the unsaturated monomer having an acidic functional group (unsaturated monomer having a hydroxyl group / unsaturated monomer having an acidic functional group) is 2.6 or less. In the present invention, the mass ratio is irrelevant to whether the acidic functional group is neutralized, and the "mass of the unsaturated monomer having an acidic functional group" is calculated as the mass of the unsaturated monomer having an acidic functional group that is not neutralized.

[0033] The non-fluorine-based oil resistant agent composition of the present invention can impart excellent oil resistance to a substrate without using a fluorine-based compound by having such a structure. In particular, the oil-resistant paper obtained by treating paper with the non-fluorine-based oil resistant agent composition of the present invention has not only excellent oil resistance (Kit method) but also excellent air permeability. The non-fluorine-based oil resistant agent composition of the present invention is described in detail below.

[0034] <Non-fluorine compounds> The non-fluorine compound contained in the non-fluorine oil resistant composition of the present invention has at least a hydrocarbon group having 1 to 60 carbon atoms and a neutralized acidic functional group in the structure. Furthermore, the proportion of the neutralized acidic functional group in the non-fluorine compound (excluding the mass of the neutralizer) is 0.4 to 21% by mass. Therefore, the non-fluorine compound can be a low molecular weight compound or a high molecular weight compound.

[0035] Among them, when the non-fluorine-based compound is a copolymer comprising structural units derived from an unsaturated monomer having a hydrocarbon group having 1 to 60 carbon atoms, an unsaturated monomer having an acidic functional group and an unsaturated monomer having a nonionic functional group, and the nonionic functional group is a hydroxyl group, the mass ratio of the monomers forming the copolymer (i.e., the mass ratio of the unsaturated monomer having a hydroxyl group as a nonionic functional group to the unsaturated monomer having an acidic functional group (unsaturated monomer having a hydroxyl group / unsaturated monomer having an acidic functional group)) is 2.6 or less.

[0036] The hydrocarbon group having 1 to 60 carbon atoms is not particularly limited, and examples thereof include monovalent aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. In addition, these functional groups may further include one or more functional groups selected from monovalent or higher aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups within the range of 1 to 60 carbon atoms. It should be noted that a part or all of the above hydrocarbon groups may be halogenated (except fluorine).

[0037] The hydrocarbon group having 1 to 60 carbon atoms can be appropriately selected according to the performance requirements. For example, from the viewpoint of improving water resistance, it preferably contains an aliphatic hydrocarbon group optionally having one or more unsaturated bonds, preferably contains a linear or branched alkyl group, and most preferably contains a linear alkyl group.

[0038] In addition, as the hydrocarbon group, a hydrocarbon group having 4 or more carbon atoms is preferably included, more preferably 8 or more, further preferably 12 or more, and most preferably 16 or more. The upper limit is preferably 50 or less, more preferably 40 or less, further preferably 30 or less, and most preferably 28 or less. A hydrocarbon group having 16 to 24 carbon atoms is particularly preferred.

[0039] Examples of the acidic functional groups include carboxyl (-COOH), sulfonic acid (-SO3H), sulfate (-OSO3H), phosphate (-OPO3H), monoester of phosphate (-OP(=O)(OH)O-), phosphonic acid (-P(=O)(OH)2), monoester of phosphonic acid (-P(=O)(OH)O-), phosphinate (-P(=O)(OH)-) and the like.

[0040] As the neutralizing agent of the above-mentioned acidic functional group, hydroxides of alkali metals and alkaline earth metals can be preferably used, and sodium hydroxide and potassium hydroxide are particularly preferred. In addition, ammonia and organic amines can also be preferably used. As organic amines, primary amines, secondary amines, and tertiary amine compounds can be used, for example, alkylamines such as monoethylamine, diethylamine, and triethylamine, amino alcohols such as monoethanolamine, diethanolamine, triethanolamine, dimethylaminoethanol, and 2-amino-2-methyl-1-propanol, and heterocyclic amines such as morpholine and piperazine can be cited. Ammonia, triethylamine, monoethanolamine, diethanolamine, triethanolamine, dimethylaminoethanol, and 2-amino-2-methyl-1-propanol can be preferably used. Two or more of the above-mentioned neutralizing agents can be used in combination.

[0041] As long as the non-fluorine compound of the present invention has at least a hydrocarbon group with 1 to 60 carbon atoms and a neutralized acidic functional group in the structure, and the proportion of the neutralized acidic functional group (excluding the mass of the neutralizing agent) is 0.4 to 21 mass %, from the viewpoint of oil resistance, as the lower limit, it is preferably 0.6 mass % or more, more preferably 0.7 mass % or more, further preferably 1.0 mass % or more, particularly preferably 1.5 mass % or more, and most preferably 2.0 mass % or more. In addition, as the upper limit, it is preferably 20 mass % or less, more preferably 19 mass % or less, further preferably 18 mass % or less, particularly preferably 17 mass % or less, and most preferably 16 mass % or less.

[0042] Among the above-mentioned non-fluorine-based compounds, as low molecular weight compounds, specifically, neutralized salts of myristic acid, palmitic acid, stearic acid, oleic acid, nonadecanoic acid, arachidic acid, heneicosanoic acid, behenic acid, tricosanoic acid, tetracosanoic acid, montanic acid, etc., neutralized salts of dialkyl sulfosuccinates such as distearyl sulfosuccinate, neutralized salts of dialkylnaphthalenesulfonic acids such as didodecylnaphthalenesulfonic acid, and neutralized salts of dialkyl phosphates such as dimyristyl phosphate, dicetyl phosphate, and distearyl phosphate.

[0043] On the other hand, when the non-fluorine-based compound is a polymer compound, a copolymer including a structural unit derived from an unsaturated monomer having a hydrocarbon group having 1 to 60 carbon atoms and an unsaturated monomer having an acidic functional group can be mentioned.

[0044] The unsaturated monomer having a hydrocarbon group having 1 to 60 carbon atoms is not particularly limited as long as it has a polymerizable unsaturated bond and a hydrocarbon group having 1 to 60 carbon atoms in its structure. For example, the polymerizable unsaturated bond and the hydrocarbon group having 1 to 60 carbon atoms may be bonded directly or through an atomic group having a valence of 2 or more.

[0045] As the unsaturated monomer having a hydrocarbon group having 1 to 60 carbon atoms, a compound represented by the following general formula (1) is preferred.

[0046] CH2=C(-X)-C(=O)-YR···(1) [In the formula, X is a hydrogen atom, a monovalent organic group (such as methyl, ethyl, etc.), a halogen atom (excluding fluorine atoms), a cyano group or a group -CH2-C(=O)-YR, Y is a divalent to tetravalent linking group having at least one group selected from -O- and -NH- or -NR-, and R is a hydrocarbon group having 1 to 60 carbon atoms. It should be noted that when Y and R exist in multiple numbers in a molecule, they may be the same or different.] In the above general formula (1), Y is preferably -Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-R'-, -Y'-R'-Y'-, -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O)-Y'-, -Y'-R'-Y'-C(=O)-Y'- or -Y'-R'-Y'-R'-, Y' is a direct bond, -O- or -NH-, and R' is -(CH2) m -(m is an integer of 1 to 5) or -C6H6-(phenylene).

[0047] As the monomer represented by the general formula (1), for example, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, tetradecyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, eicosyl (meth)acrylate, behenyl (meth)acrylate, and the like can be preferably used. (Meth)acrylates having a cyclic hydrocarbon group as described in paragraphs 0027 to 0030 of JP-A-2019-26746 can also be used, for example, cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, and the like can be mentioned.

[0048] In addition, the "α-substituted acrylate" disclosed in Japanese Patent Application Laid-Open No. 2017-66325 can be preferably used. For example, butyl α-chloroacrylate, lauryl α-chloroacrylate, stearyl α-chloroacrylate, eicosyl α-chloroacrylate, behenyl α-chloroacrylate, methyl α-cyanoacrylate, ethyl α-cyanoacrylate, butyl α-cyanoacrylate, octyl α-cyanoacrylate, lauryl α-cyanoacrylate, stearyl α-cyanoacrylate, eicosyl α-cyanoacrylate, behenyl α-cyanoacrylate, etc. can be preferably used.

[0049] Furthermore, acrylic monomers among the “amide group-containing monomers” disclosed in International Publication No. 2019 / 026593 and Japanese Patent Application Laid-Open No. 2019-26747 can be used. For example, lauric acid amide ethyl (meth) acrylate, myristic acid amide ethyl (meth) acrylate, palmitic acid amide ethyl (meth) acrylate, stearic acid amide ethyl (meth) acrylate, behenic acid amide ethyl (meth) acrylate, lauryl (meth) acrylamide, cetyl (meth) acrylamide, stearyl (meth) acrylamide, behenyl (meth) acrylamide, etc. can be preferably used.

[0050] In addition, the "monomer containing a carbamate group or a urea group" disclosed in Japanese Unexamined Patent Publication No. 2019-26746 and Japanese Translation of ...

[0051] As the monomer represented by the general formula (1), the “monomer derived from itaconic acid” disclosed in International Publication No. 2016 / 178429 can be used, and for example, dimethyl itaconate, distearyl itaconate, etc. can be preferably used.

[0052] As monomers other than the general formula (1), monomers described in paragraphs 0016 to 0034 of JP-A-2017-538793 can be used, and for example, sorbitan tristearate methacrylate (described in paragraph 0077), sorbitan tristearate urethane methacrylate (described in paragraph 0078), sorbitan tristearate urethane styrene monomer (described in paragraph 0079), sorbitan trioleate methacrylate (described in paragraph 0080) and the like can be preferably used.

[0053] As a monomer other than the above-mentioned general formula (1), a “sulfonamide group-containing monomer” disclosed in JP-A-2021-014482 can be used, and a compound represented by the following general formula (2) can be preferably used.

[0054] CH2=CA 1 -C(=O)-OR 1 -A 2 -R 2 ···(2) [Wherein, A 1 is a hydrogen atom, a methyl group, a chlorine atom, a bromine atom or an iodine atom, A 2 is -NH-SO2- or -SO2-NH-, R 1 is a hydrocarbon group having 1 to 5 carbon atoms, R 2 It is a hydrocarbon group having 1 to 60 carbon atoms.] For example, a compound represented by the following general formula (3) can be preferably used.

[0055] CH2=CHC(=O)OC2H4NHSO2C 18 H 37 ···(3) In addition, as monomers other than those represented by general formulae (1) to (2), monomers other than acrylic acid in the “amide group-containing monomers” disclosed in International Publication No. 2019 / 026593 can be used. For example, palmitic acid amide ethyl vinyl ether, stearic acid amide ethyl vinyl ether, palmitic acid amide ethyl allyl ether, and stearic acid amide ethyl allyl ether can be preferably used.

[0056] As monomers other than those represented by the general formulae (1) to (2), “carbonate group-containing monomers” can be used, and for example, allyl methyl carbonate, allyl ethyl carbonate, allyl phenyl carbonate, etc. can be preferably used.

[0057] In addition, as monomers other than those represented by general formulae (1) to (2), “vinyl ester monomers” may be used, for example, vinyl acetate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl octanoate, vinyl laurate, vinyl stearate, vinyl benzoate, and vinyl chloroacetate.

[0058] As monomers other than those represented by the general formulae (1) to (2), “olefin monomers” may be used, such as propylene, 1-butene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-octadecene, styrene, α-methylstyrene, and the like.

[0059] As monomers other than those of the general formulae (1) to (2), "silicone-based monomers" may be used. For example, monomers having a hydrocarbon group having 1 to 60 carbon atoms and having an unsaturated group such as a vinyl group or a (meth)acrylic group at the terminal and / or in the side chain may be used. Specifically, single-terminal (meth)acrylic-modified silicones and dual-terminal (meth)acrylic-modified silicones may be used.

[0060] The above-mentioned unsaturated monomer having a hydrocarbon group having 1 to 60 carbon atoms may be used alone or in combination of two or more.

[0061] In the non-fluorine-based compound of the present invention, based on the total amount of monomer components constituting the non-fluorine-based compound (excluding the mass of the neutralizer), the content of unsaturated monomers having a hydrocarbon group having 1 to 60 carbon atoms may be 30% by mass or more. From the viewpoint of more appropriately achieving the effect of the present invention, it is preferably 30 to 99.5% by mass, more preferably 40 to 99% by mass, further preferably 45 to 97% by mass, and most preferably 50 to 96% by mass.

[0062] Examples of the unsaturated monomer having an acidic functional group that can be used in the present invention include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, vinyl sulfonic acid, (meth)allyl sulfonic acid, vinylbenzenesulfonic acid, acrylamide tert-butylsulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid, 2-methacrylamide-2-ethylpropanesulfonic acid, 2-acrylamide butanesulfonic acid, and 2-(meth)acryloyloxyethyl acid phosphate.

[0063] In the non-fluorine-based compound of the present invention, the content of the unsaturated monomer having an acidic functional group is 0.5% by mass or more based on the total amount of the monomer components constituting the non-fluorine-based compound (excluding the mass of the neutralizing agent). From the viewpoint of more appropriately achieving the effect of the present invention, it is preferably 1 to 60% by mass, more preferably 3 to 55% by mass, and further preferably 4 to 50% by mass.

[0064] The non-fluorine-based compound of the present invention may contain a structural unit derived from an unsaturated monomer having a nonionic functional group in addition to an unsaturated monomer having a hydrocarbon group having 1 to 60 carbon atoms and an unsaturated monomer having an acidic functional group.

[0065] Specific examples of the nonionic functional group include a hydroxyl group, a phenolic hydroxyl group, a nitrile group, an amide group, a (thio)urethane group, a (thio)urea group, a (thio)carbonate group, and an ester group.

[0066] Specific examples of the monomer having a hydroxyl group among the unsaturated monomers having a nonionic functional group include 2-hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-allyloxypropyl (meth)acrylate, 2-(meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-allyloxypropyl (meth)acrylate, 2-(meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-allyloxypropyl (meth)acrylate, 2-(meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-allyloxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-allyloxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-phenyl ... Acrylic monomers such as acryloxyethyl-2-hydroxyethyl-phthalic acid, glycerol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, N-(hydroxymethyl)(meth)acrylamide, N-(2-hydroxyethyl)(meth)acrylamide; allyl monomers such as allyl alcohol, 3-allyloxy-1,2-propylene glycol, ethylene glycol monoallyl ether, triallyl citrate; vinyl monomers such as 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, etc.

[0067] Specific examples of the monomer having a phenolic hydroxyl group among the above-mentioned unsaturated monomers having a nonionic functional group include 4-hydroxyphenyl (meth)acrylate, N-(4-hydroxyphenyl) (meth)acrylamide, 2-(2,3-dihydroxyphenoxy)ethyl (meth)acrylate, ω-(2,3-dihydroxyphenoxy)polyethylene glycol (meth)acrylate, 2-(2,3-dihydroxyphenoxycarbonylamino)ethyl (meth)acrylate, ω-(2,3-dihydroxyphenoxycarbonylamino)polyethylene glycol (meth)acrylate, and the like.

[0068] Specific examples of the monomer having a nitrile group among the unsaturated monomers having a nonionic functional group include (meth)acrylonitrile, 2-ethylacrylonitrile, 2-propylacrylonitrile, 2-chloroacrylonitrile, and 2-butenenitrile.

[0069] Among the unsaturated monomers having a nonionic functional group, the monomer having an amide group is not particularly limited as long as it has an amide group in the structure, but does not have a monovalent hydrocarbon group having 1 to 60 carbon atoms. Specific examples thereof include (meth)acrylamide, N,N'-methylenebis(meth)acrylamide, diacetone(meth)acrylamide, N-vinyl-2-caprolactam having a cyclic structure, and N-vinyl-2-pyrrolidone.

[0070] Among the unsaturated monomers having a nonionic functional group, the monomer having a (thio)carbamate group is not particularly limited as long as it has a (thio)carbamate group in its structure, but does not have a monovalent hydrocarbon group having 1 to 60 carbon atoms. For example, commercially available products include urethane acrylate AH-600 (manufactured by Kyoeisha Chemical Co., Ltd.: phenyl glycidyl ether acrylate hexamethylene diisocyanate urethane prepolymer), urethane acrylate UA-306H (manufactured by Kyoeisha Chemical Co., Ltd.: pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer), urethane acrylate UA-306T (manufactured by Kyoeisha Chemical Co., Ltd.: pentaerythritol triacrylate toluene diisocyanate urethane prepolymer), urethane acrylate UA-306I (manufactured by Kyoeisha Chemical Co., Ltd.: pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer), and urethane acrylate UA-510H (manufactured by Kyoeisha Chemical Co., Ltd.: dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer).

[0071] Among the unsaturated monomers having a nonionic functional group, the monomer having a (thio)urea group is not particularly limited as long as it has a (thio)urea group in its structure, but does not have a monovalent hydrocarbon group having 1 to 60 carbon atoms. Examples thereof include 2-(2-oxoimidazolidin-1-yl)ethyl (meth)acrylate and the like.

[0072] Among the unsaturated monomers having a nonionic functional group, the monomer having a (thio)carbonate group is not particularly limited as long as it has a (thio)carbonate group in its structure, but does not have a monovalent hydrocarbon group having 1 to 60 carbon atoms. Examples thereof include (2-oxo-1,3-dioxolan-4-yl)methyl methacrylate.

[0073] Among the unsaturated monomers having a nonionic functional group, the monomer having an ester group is not particularly limited as long as it has an ester group in the structure, but does not have a monovalent hydrocarbon group having 1 to 60 carbon atoms. Examples thereof include 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, and γ-butyrolactone (meth)acrylate, which is a substance having a cyclic structure.

[0074] Alternatively, the monomer may have two or more of these nonionic functional groups in its structure. Examples thereof include monomers having a carbonate group, a urethane group, or an ester group obtained by reacting a polycarbonate diol with a diisocyanate or a hydroxyalkyl (meth)acrylate.

[0075] The content of the unsaturated monomer having a nonionic functional group in the molecule is preferably 0.1 to 69.5% by mass, more preferably 1 to 60% by mass, and further preferably 3 to 50% by mass, based on the total amount of monomer components constituting the non-fluorine-based compound (excluding the mass of the neutralizer). When used within this range, the oil resistance can be further improved.

[0076] It should be noted that in the non-fluorine-based oil resistant composition of the present invention, from the viewpoint of oil resistance, when the non-fluorine-based compound is a copolymer containing structural units derived from an unsaturated monomer having a hydrocarbon group having 1 to 60 carbon atoms, an unsaturated monomer having an acidic functional group, and an unsaturated monomer having a nonionic functional group, and the unsaturated monomer having a nonionic functional group is an unsaturated monomer having a hydroxyl group as a nonionic functional group, the mass ratio of the unsaturated monomer having a hydroxyl group to the unsaturated monomer having an acidic functional group (unsaturated monomer having a hydroxyl group / unsaturated monomer having an acidic functional group) is 2.6 or less. As described above, in the present invention, this mass ratio is irrelevant to the presence or absence of neutralization of the acidic functional group, and the "mass of the unsaturated monomer having an acidic functional group" is calculated as the mass of the unsaturated monomer having an acidic functional group that has not been neutralized.

[0077] The non-fluorine-based compound of the present invention may contain unsaturated monomers other than the unsaturated monomer having a hydrocarbon group having 1 to 60 carbon atoms, the unsaturated monomer having an acidic functional group, and the unsaturated monomer having a nonionic functional group.

[0078] Examples of such other unsaturated monomers include ethylene, vinyl chloride, vinylidene chloride, allylamine, diallylamine, vinyl-modified silica, (meth)acrylic acid-modified silica, etc. These monomers may be used alone or in combination of two or more.

[0079] From the perspective of easy handling of the substrate, the non-fluorine compound is preferably prepared in a form dissolved or dispersed in a medium such as water or an organic solvent. It should be noted that due to the influence of the physical properties (solubility, melting point, etc.) of the non-fluorine compound as the dispersoid, the state of the dispersoid (solid, liquid) is sometimes different and sometimes difficult to determine depending on the temperature (manufacturing temperature, storage temperature) of the oil-resistant composition. Therefore, for "dispersion", "emulsification" or similar expressions in this specification, unless otherwise specified, the emulsified state, the suspended state, etc. are not clearly distinguished.

[0080] Examples of the medium include water; aliphatic alcohols such as methanol, ethanol, isopropanol, isobutanol, hexanol, and 2-ethylhexanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, and diacetone alcohol; esters such as ethyl acetate, methyl acetate, butyl acetate, methyl lactate, and ethyl lactate; ethers such as diethyl ether, diisopropyl ether, methyl cellosolve, ethyl cellosolve, dioxane, and methyl tert-butyl ether; ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Diols such as dipropylene glycol; glycol ethers such as ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-3-methyl-1-butanol; glycol esters such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether acetate; amides such as formamide, acetamide, benzamide, N,N-dimethylformamide, and acetanilide, one of which can be used alone or in combination of two or more. Although there is no particular restriction, from the perspective of operational safety and environmental load when treating the substrate, water is preferably used as the main body. From the perspective of the specifications of the manufacturing device, damage to the base agent, etc., when it is impossible to set a sufficient drying temperature and time, a highly volatile organic solvent such as ethanol can also be used as the main body.

[0081] The non-fluorine compound can be dissolved or dispersed in a medium by a known method. For example, a homomixer, a homogenizer, a high pressure homogenizer, an ultrasonic homogenizer and the like can be used. In addition, the non-fluorine compound can be made self-dispersible, and a surfactant can also be added as a dispersant.

[0082] The content of the dispersant can be appropriately selected in consideration of oil resistance and dispersion stability of the oil resistant composition. For example, it is preferably 0.01 to 40 parts by mass, more preferably 0.1 to 30 parts by mass, further preferably 0.3 to 20 parts by mass, and most preferably 0.5 to 15 parts by mass, relative to 100 parts by mass of the non-fluorine-based compound, in terms of solid content.

[0083] As the dispersant, a known dispersant may be used. Examples thereof include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. One type may be used alone, or two or more types may be used in combination.

[0084] As anionic surfactants, for example, various fatty acid salts, alkylbenzene sulfonates, alkane sulfonates, alkyl sulfate ester salts, alkyl phosphate ester salts, polyoxyethylene alkyl ether sulfates, polyoxyethylene substituted phenyl ether sulfates, polycarboxylates, etc. can be used, and counter ions include sodium, potassium, calcium, ammonium, triethanolamine, etc., but are not limited to these.

[0085] Examples of the nonionic surfactant include fatty acid esters such as various higher fatty acid glycerides, polyoxyethylene alkyl ethers, polyoxypropylene alkyl ethers, polyoxyethylene fatty acid esters, fatty acid alkanolamides, alkyl glucosides, higher alcohols, Pluronic emulsifiers, and alkyl dimethylamine-N-oxides, but are not limited thereto.

[0086] As the cationic surfactant, for example, in addition to quaternary salts such as various alkyltrimethylammonium salts, alkyldimethylbenzylammonium salts, dialkyldimethylammonium salts, alkylpyridinium chloride salts, and quaternary compounds of polyoxyethylene alkylamines, amine salts obtained by neutralizing amines such as alkylamine salts, alkyldimethylamine salts, and polyoxyethylene alkylamine salts with appropriate acids can also be used. As counterions, chloride ions, bromide ions, sulfate ions, formate ions, acetate ions, methylsulfate ions, and ethylsulfate ions can be cited, but are not limited to these.

[0087] Examples of the amphoteric surfactant include, but are not limited to, alkyl betaine type amphoteric surfactants, amide betaine type amphoteric surfactants, sulfo betaine type amphoteric surfactants, phosphate betaine type amphoteric surfactants, imidazoline betaine type amphoteric surfactants, alkyl amine oxide type amphoteric surfactants, amino acid type amphoteric surfactants, and phosphate ester type amphoteric surfactants.

[0088] The non-fluorine-based compound of the polymer compound type can be manufactured by copolymerizing the above-mentioned monomers using various polymerization methods (free radical polymerization, cationic polymerization, anionic polymerization) such as known bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, and radiation polymerization. As emulsion polymerization methods, for example, a one-time monomer addition method in which the monomer is added once, a monomer drop addition method in which the monomer is added continuously, etc. can be cited. In addition, polymerization can also be carried out after mechanical treatment using a high-pressure homogenizer, etc. In addition, in the case of solution polymerization, for example, water can be added after polymerization and then the solvent can be removed so that the copolymer is dispersed in water. It is not necessary to add a dispersant, and a self-dispersing liquid can be manufactured.

[0089] The dispersant that can be used during polymerization is not particularly limited, and examples thereof include the anionic surfactant, the nonionic surfactant, the cationic surfactant, the amphoteric surfactant, and a reactive surfactant (a reactive anionic surfactant, a reactive nonionic surfactant, a reactive cationic surfactant, and a reactive amphoteric surfactant that are reactive with the monomer). These may be used alone or in combination of two or more.

[0090] As the reactive surfactant, in addition to polyethylene glycol mono(meth)acrylates of various molecular weights (different EO addition mole numbers), polyoxyethylene alkylphenyl ether (meth)acrylates, 2-(meth)acryloyloxyethyl ammonium sulfonate, polyethylene glycol monomaleate and its derivatives, (meth)acryloyl polyoxyalkylene alkyl ether phosphates, reactive surfactants described in paragraphs 0074 to 0094 of JP-A-2017-155095 and the like can be mentioned.

[0091] As the polymerization initiator, known polymerization initiators such as azo, peroxide or redox can be used appropriately. The content of the polymerization initiator is, for example, preferably 0.01 to 10 parts by mass, more preferably 5 parts by mass or less, and particularly preferably 2 parts by mass or less, relative to 100 parts by mass of all monomers constituting the above-mentioned non-fluorine-based compound. In addition, by using ammonium persulfate, sodium persulfate, etc., acidic functional groups can also be introduced into the polymer.

[0092] In the polymerization reaction, a chain transfer agent or a polymerization inhibitor such as dodecyl mercaptan, tert-butyl alcohol, or thioglycolic acid may be used to adjust the molecular weight.

[0093] In addition, by using a polymer compound (including an oligomer) having a mercapto group, a structure derived from the polymer compound can be introduced into a non-fluorine compound to produce a block copolymer or a graft copolymer. Examples of such a polymer compound include mercapto-modified silicone and mercapto-amino-modified silicone.

[0094] The polymerization reaction temperature can be appropriately selected, and is preferably 20°C to 150°C, for example.

[0095] In the polymerization reaction, the weight average molecular weight of the obtained non-fluorine-based compound can be adjusted by increasing or decreasing the amount of the polymerization initiator, chain transfer agent, and polymerization inhibitor used and by adjusting the polymerization temperature.

[0096] The monomer concentration during polymerization is preferably 10 to 70% by mass, more preferably 15 to 60% by mass, from the viewpoint of reaction control and operability.

[0097] When an organic solvent is used in producing the oil proofing agent composition, a removal step may be provided as necessary, for example, a method of heating under normal pressure or reduced pressure may be mentioned.

[0098] The dispersion of the non-fluorine-based oil repellent composition used in the present invention is preferably subjected to an operation of removing residual monomers, residual polymerization initiators, etc., as necessary, in order to reduce unreacted monomers, unreacted polymerization initiators, and the like.

[0099] Specifically, examples of methods for removing residual monomers from the polymerization system include a method of passing steam through a tank containing the acrylic resin emulsion and a so-called steam stripping method of bringing the acrylic resin emulsion into countercurrent contact with steam in a multi-stage tower.

[0100] The non-fluorine-based oil resistant agent composition of the present invention can be used as a treatment liquid or as a stock solution, and the solid content concentration can be appropriately selected according to the treatment method, operability, etc. For example, the solid content concentration is preferably about 0.01 to 70% by mass, more preferably about 0.5 to 60% by mass, particularly preferably about 0.7 to 50% by mass, and most preferably about 0.9 to 40% by mass.

[0101] In the non-fluorine-based oil-resistant composition of the present invention, additives may be added as needed. Examples of additives include other oil-resistant agents, water repellents, paper strength agents, sizing agents, pigments, penetrants, defoamers, pH adjusters, antibacterial agents, antifungal agents, colorants, antioxidants, deodorants, various organic solvents, chelating agents, antistatic agents, catalysts, crosslinking agents, antibacterial and deodorizing agents, flame retardants, softeners, and anti-wrinkle agents.

[0102] Examples of defoamers include: oil-based defoamers such as castor oil, sesame oil, linseed oil, and animal and vegetable oils; fatty acid-based defoamers such as stearic acid, oleic acid, and palmitic acid; fatty acid ester-based defoamers such as isoamyl stearate, distearyl succinate, ethylene glycol distearate, and butyl stearate; alcohol-based defoamers such as polyoxyalkylene monool di-tert-amylphenoxyethanol, 3-heptanol, and 2-ethylhexanol; ether-based defoamers such as di-tert-amylphenoxyethanol, 3-heptyl cellosolve, nonyl cellosolve, and 3-heptyl carbitol; phosphate-based defoamers such as tributyl phosphate and tris(butoxyethyl) phosphate; amine-based defoamers such as diamylamine; amide-based defoamers such as polyalkylene amides and acylated polyamines; sulfate-based defoamers such as sodium lauryl sulfate; mineral oil, etc. The defoamers may be used alone or in combination of two or more.

[0103] As the antistatic agent, an antistatic agent that is not likely to hinder oil resistance can be used. As the antistatic agent, for example, anionic antistatic agents such as higher alcohol sulfate ester salts, sulfated oils, and sulfonates, cationic antistatic agents such as quaternary ammonium salts and imidazoline quaternary salts, nonionic antistatic agents such as polyethylene glycol and polyol ester types, amphoteric antistatic agents such as imidazoline quaternary salts, alanine and betaine types, charge-controlling polymers of polymer compounds, polyalkylamines, etc. The antistatic agent can be used alone or in combination of two or more.

[0104] By attaching the non-fluorine-based oil-proofing agent composition of the present invention to a substrate and drying it, excellent oil resistance can be imparted. When the substrate is paper, in addition to oil resistance, extremely excellent air permeability is also exhibited. That is, the oil-resistant product of the present invention is a product in which the non-fluorine-based compound is present on at least one of the surface and the interior of the substrate. In addition, as described later, the oil-resistant paper of the present invention is an oil-resistant paper containing the non-fluorine-based compound, preferably an oil-resistant paper having a kit value of 1 to 6 for the plane portion of the oil-resistant paper measured according to the provisions of TAPPI UM-557.

[0105] <Oil-resistant paper> (Paper substrate) The paper substrate used in the oil-proof paper of the present invention is not particularly limited, and any paper substrate used in known oil-proof paper can be used. Examples of the paper substrate include uncoated paper and coated paper.

[0106] Examples of uncoated paper include paper made by using one type of pulp alone or by mixing two or more types of pulp at any blending ratio.

[0107] Examples of the pulp include coniferous bleached kraft pulp (NBKP), broadleaved bleached kraft pulp (LBKP), groundwood pulp (GP), thermomechanical pulp (TMP), chemical thermomechanical pulp (CTMP), and deinked pulp (DIP).

[0108] As pulp, pulp having a Canadian Standard Freeness (CSF) adjusted to 350 to 550 mL is preferred. If the CSF of the pulp is 350 mL or more, oil resistance is easily exhibited. If the CSF of the pulp is 550 mL or less, the paper strength is sufficient. The CSF of the pulp can be adjusted by beating the pulp. When using two or more types of pulp, the CSF can be adjusted by mixing the pulps that have been beaten separately, or by beating the pre-mixed pulps to adjust the CSF.

[0109] The paper substrate may contain a filler. Examples of the filler include fillers used in conventional papermaking. Examples of the filler include inorganic fillers such as kaolin, calcined kaolin, delaminated kaolin, illite, heavy calcium carbonate, light calcium carbonate, light calcium carbonate-silicon dioxide composite, magnesium carbonate, barium carbonate, titanium dioxide, zinc oxide, silicon oxide, amorphous silicon dioxide, aluminum hydroxide, calcium hydroxide, and magnesium hydroxide. The filler may be used alone or in combination of two or more.

[0110] The paper substrate may be unsized paper, or may have a sizing agent added internally or externally.

[0111] As the sizing agent, in the case of acidic papermaking, rosin-based sizing agents, rosin emulsion-based sizing agents, α-carboxymethyl saturated fatty acids, etc. can be cited. In the case of neutral papermaking, rosin-based sizing agents for neutral papermaking, alkyl ketene dimers, alkenyl succinic anhydrides, cationic polymer-based sizing agents, etc. can be cited. The amount of sizing agent added is not particularly limited. In external addition using a sizing press, etc., a surface sizing agent (rosin-based sizing agent, synthetic resin-based sizing agent, etc.) can be used.

[0112] Furthermore, from the viewpoint of improving the oil resistance of the oil-resistant paper of the present invention, the paper base material preferably contains a cationic polymer.

[0113] Examples of the cationic polymer include cationic paper strength enhancers used in conventional papermaking. Examples of the cationic polymer include polyamine epichlorohydrin resins, polyamide epichlorohydrin resins, cationized starch, cationic polyacrylamide (acrylamide-allylamine copolymers, acrylamide-dimethylaminoethyl (meth)acrylate copolymers, acrylamide-diethylaminoethyl (meth)acrylate copolymers, acrylamide-quaternized dimethylaminoethyl (meth)acrylate copolymers, acrylamide-quaternized diethylaminoethyl (meth)acrylate copolymers, etc.), cationically modified polyvinyl alcohol, polydiallyldimethylammonium chloride, polyallylamine, polyvinylamine, polyethyleneimine, N-vinylformamide-vinylamine copolymers, melamine resins, polyamide epoxy resins, etc.

[0114] As the cationic polymer, from the viewpoint of excellent oil resistance of the obtained oil-proof paper, polyamine epichlorohydrin resin, polyamide epichlorohydrin resin, cationized starch, cationic polyacrylamide, polyethyleneimine, etc. are preferred. The cationic polymer may be used alone or in combination of two or more.

[0115] The content of the cationic polymer contained in the paper base material preferably satisfies the relationship of the following formula (I), and more preferably satisfies the relationship of the following formula (II).

[0116] 1≤D×(C / 100)≤120···(I) 3≤D×(C / 100)≤60···(II) Here, D is the cationic charge density (μeq / g) of the cationic polymer, and C is the content ratio (mass %) of the cationic polymer relative to the pulp (100 mass %) constituting the paper base material.

[0117] D×(C / 100) (μeq / g) is an index of the cationization of the paper substrate. If D×(C / 100) is above the lower limit of the above range, the cationicity of the paper substrate becomes sufficiently high, and the non-fluorine-based compound is more fully fixed to the surface of the paper substrate. Therefore, the oil resistance of the obtained oil-resistant paper is more excellent. If D×(C / 100) is below the upper limit of the above range, the fixation of the non-fluorine-based compound is sufficient, and a large amount of cationic polymers is not required, so the manufacturing cost of the oil-resistant paper can be suppressed.

[0118] The paper substrate may contain other concurrent agents other than fillers, sizing agents, and cationic polymers within a range that does not impair the effects of the present invention. Examples of other concurrent agents include fixing agents, dry paper strength agents, wet paper strength agents, aluminum sulfate, yield improvers, dyes, pigments, and the like. Other concurrent agents may be used alone or in combination of two or more.

[0119] The paper substrate can be appropriately produced by a known papermaking machine. The papermaking conditions are not particularly limited. Examples of the papermaking machine include a fourdrinier papermaking machine, a twin-wire papermaking machine, and a cylinder papermaking machine.

[0120] In the present invention, coated paper having a pigment coating layer provided on at least one surface of the above-mentioned paper substrate can also be used as the paper substrate.

[0121] As the paper substrate, a paper substrate subjected to calendering treatment may be used.

[0122] <Method for producing oil-resistant paper> As a method for treating the non-fluorine-based oil repellent composition of the present invention on a paper substrate, known methods such as coating, size press, and internal addition to a pulp slurry may be employed, and methods similar to coating and size press are particularly preferred.

[0123] The treatment amount of the non-fluorine-based oil-proofing agent composition of the present invention is not particularly limited. From the viewpoint of oil resistance, for example, the amount of the non-fluorine-based compound present (adherence) relative to the paper substrate is preferably 0.5 to 30 g / m 2 More preferably, it is 1 to 20 g / m 2 More preferably, it is 1.5 to 15 g / m 2 About 2 to 10 g / m 2 From the viewpoint of air permeability, dry load after treatment, and cost, 15 g / m 2 the following.

[0124] The oil-resistant paper of the present invention can be said to have oil resistance if the Kit value of the flat surface of the oil-resistant paper measured according to the provisions of TAPPI UM-557 is 1 or more. Although it depends on the performance requirements in the application, for example, when oil-resistant paper is used to wrap food, the Kit value is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, and particularly preferably 4 or more for the purpose of reducing the penetration of oil to the opposite side.

[0125] The oil-proof paper of the present invention may have water resistance according to performance requirements such as printability, and can be said to have water resistance if the Stockigt sizing degree measured according to JISP-8122:2004 is 2 seconds or more, preferably 5 seconds or more, and more preferably 10 to 500 seconds.

[0126] The greaseproof paper of the present invention preferably has a Gurley air permeability of 1000 seconds or less, more preferably 500 seconds or less, and particularly preferably 100 seconds or less, as measured in accordance with JIS P-8117: 2009. If the Gurley air permeability of the greaseproof paper exceeds 1000 seconds, the flavor and storage stability of food packaged with the greaseproof paper may be reduced.

[0127] As a method for treating a paper substrate with a non-fluorine-based oil-proofing agent composition, it can be implemented by using a known coating machine. As a coating machine, a size press, a coating machine, a printing machine, etc. can be cited. As a size press, a double-roll size press, a film transfer size press, a calendering size press, etc. can be cited. As a coating machine, a roll coater, an air knife coater, a slit coater, a gear coater, a blade coater, a rod blade coater, a bill blade coater, a short dwell blade coater, a rod coater, a curtain coater, a direct gravure coater, an offset gravure coater, etc. can be cited. As a printing machine, a gravure printing machine, a flexographic printing machine, an offset printing machine, etc. can be cited.

[0128] A drying process can be provided after the non-fluorine-based oil-resistant agent composition is attached to the paper substrate. It can be dried by natural drying, but it is preferably dried by heating. For example, as the general drying temperature when using the above-mentioned well-known coater, it is preferably lower than 120 °C, more preferably 80 to 110 °C, and further preferably 90 to 110 °C.

[0129] A calendering process can be provided after the non-fluorine-based oil-resistant agent composition is attached to the paper substrate. Examples of the calender include a super calender and a soft calender.

[0130] Through the above manufacturing method, the oil-resistant paper of the present invention can be appropriately manufactured.

[0131] It should be noted that in the present invention, oil-resistant products can also be manufactured by treating films, fibers, woven fabrics, non-woven fabrics, etc. other than paper, which is used as the substrate, with the non-fluorine-based oil-resistant agent composition of the present invention.

[0132] Examples Hereinafter, the oil-resistant paper using the non-fluorine-based oil-resistant agent composition of the present invention will be specifically described as the center, but the present invention is not limited to these examples. In addition, unless otherwise specified, "parts" and "%" in the examples represent "parts by mass" and "mass %".

[0133] 〔Oil resistance test〕 <TAPPI KIT method> According to the provisions of TAPPI UM-557, a test solution with different mixing ratios of 1 drop of castor oil, toluene, and n-heptane (the mixing ratio of the Kit number in Table 1 below) is dropped onto the surface of the oil-resistant paper. After 15 seconds, the change in the color of the surface of the oil-resistant paper caused by the penetration of the test solution is visually evaluated. The result of the test is represented by the number of the test solution with the largest number in the test solution whose surface color does not darken (Kit value). The larger the number, the more excellent the oil resistance.

[0134] [Table 1]

[0135] Paper specimens (2.5 cm × 3.5 cm) are cut out from the oil-resistant paper, and the oil resistance of the oil-resistant agent coating plane part of the oil-resistant paper is measured according to the above criteria.

[0136] <Water resistance test method> The water resistance of the oil-resistant paper is evaluated for the Stockigt sizing degree according to the provisions of JIS P 8122:2004.

[0137] <Manufacture of oil-resistant paper> The following paper substrates were treated with the oil-proofing agent composition to produce oil-proof papers of Examples 1 to 37 and Comparative Examples 1 to 14. Then, the above-mentioned oil-proof test was performed on each oil-proof paper.

[0138] (Paper substrate) ·Base paper A (no chemicals added) As raw material pulp, LBKP (bleached kraft pulp of broadleaf trees) and NBKP (bleached kraft pulp of coniferous trees) were used. LBKP and NBKP were mixed at a mass ratio of 70:30 and beaten with a pulper until the CSF reached 440 mL. After obtaining a pulp slurry, the basis weight was 40 g / m 2 The paper was made in the manner of 2 The Stockigt sizing of the obtained paper substrate was 0 seconds. In addition, the air permeability was 2 seconds.

[0139] ·Base paper B (with moist paper strength enhancer added) As raw material pulp, LBKP (bleached kraft pulp of broadleaf trees) and NBKP (bleached kraft pulp of coniferous trees) were used. LBKP and NBKP were mixed at a mass ratio of 70:30 and beaten with a beater until the CSF reached 440 mL to obtain a pulp slurry. After adding a wet paper strength enhancer (trade name: "FW-7281" manufactured by Seiko PMC Co., Ltd., an aqueous solution of polyamine epichlorohydrin resin; solid content concentration 25%) at a mass ratio of 0.4% relative to the pulp (solid content), the pulp slurry was mixed and stirred until the basis weight reached 40 g / m 2 The paper was made in the manner of 2 The Stockigt sizing of the obtained paper substrate was 0 seconds. In addition, the air permeability was 2 seconds.

[0140] Base paper C (with moist paper strength enhancer and sizing agent added) As raw material pulp, LBKP (bleached kraft pulp of broadleaf trees) and NBKP (bleached kraft pulp of coniferous trees) were used. LBKP and NBKP were mixed at a mass ratio of 70:30 and beaten with a pulper until the CSF reached 440 mL to obtain a pulp slurry. To the pulp slurry, 1.0 mass % of rosin sizing agent was added relative to the pulp, the pH of the pulp slurry was adjusted to 5.0 with aluminum sulfate, and 0.4 mass % of a wet paper strength enhancer (trade name: "FW-7281" manufactured by Seikyo PMC Co., Ltd., an aqueous solution of polyamine epichlorohydrin resin; solid content concentration 25%) was further added relative to the pulp (solid content), and the basis weight was 40 g / m 2 The paper was made in the manner of 2 The Stockigt sizing of the obtained paper substrate was 10 seconds. In addition, the air permeability was 2 seconds.

[0141] (Processing method) Size press A double roll size press was used as a coating machine to adhere the oil-proofing agent composition to the paper substrate, and then dried at 105° C. for 1 minute using a rotary dryer. It should be noted that the "drying treatment amount" described in the table is calculated using the mass change (wet pick up) of the oil-proofing agent composition before and after adhesion of the paper substrate and the content of the non-fluorine-based compound in the composition.

[0142] ·Rod coating The oil-proofing agent composition was applied to the paper substrate using a Meyer rod and dried at 110°C for 5 minutes using a hot air dryer. The same treatment was repeated as needed to achieve the "drying treatment amount" described in the table. It should be noted that the "drying treatment amount" described in the table is calculated using the mass change (wet slurry absorption rate) of the oil-proofing agent composition before and after attachment of the paper substrate and the content of the non-fluorine-based compound in the composition.

[0143] ·Method for producing non-fluorine-based oil resistant composition With respect to Production Examples 1 to 23 and Comparative Production Examples 1 and 2, oil resistant agent compositions were produced by any of the following methods under the conditions described in the table.

[0144] (Method A) Each monomer, polymerization initiator, chain transfer agent, surfactant, and polymerization medium were added to a reaction vessel, stirred and heated under a nitrogen atmosphere to perform free radical polymerization. Then, the concentration was adjusted using ion exchange water so as to achieve the polymer content described in the table to obtain a water-based oil-proofing agent composition.

[0145] (Method B) Each monomer, surfactant, and polymerization medium were mixed in a reaction vessel, and the obtained mixed solution was treated with a high-pressure homogenizer (400 bar). Then, a polymerization initiator and a chain transfer agent were added, and the mixture was stirred and heated under a nitrogen atmosphere to perform free radical polymerization. Then, the concentration was adjusted using ion exchange water so as to obtain the polymer content ratio described in the table, and a water-based oil-proofing agent composition was obtained.

[0146] (Method C) Each monomer, polymerization initiator, chain transfer agent, and polymerization medium were added to the reaction container, stirred and heated under a nitrogen atmosphere to perform free radical polymerization. Then, while maintaining the internal temperature, a 4.8% sodium hydroxide aqueous solution was added in a manner to achieve the neutralization degree recorded in the table, and then, ion exchange water was appropriately added to adjust the viscosity, and the organic solvent was distilled off. Then, the concentration was adjusted using ion exchange water in a manner to achieve the polymer content rate recorded in the table to obtain a water-based oil-proofing agent composition.

[0147] (Production Example 15) Each monomer, polymerization initiator, polymerization medium, and triethanolamine (10.8 parts) were added to a reaction container, stirred and heated under a nitrogen atmosphere to perform free radical polymerization. Then, ion exchange water was appropriately added to adjust the viscosity, and the organic solvent was distilled off. Then, the concentration was adjusted using ion exchange water so as to achieve the polymer content described in the table to obtain a water-based oil-proofing agent composition.

[0148] <Abbreviation in the table> MMA: Methyl Methacrylate EA: Ethyl acrylate BA: Butyl acrylate BI-HEA: 2-[(Butylcarbamoyl)oxy]ethyl acrylate ※The reaction product of butyl isocyanate and 2-hydroxyethyl acrylate EHA: 2-Ethylhexyl Acrylate LA: Lauryl acrylate SA: Stearyl acrylate SMA: Stearyl Methacrylate AA: Acrylic acid MAA: Methacrylic acid AAMPS: 2-Acrylamido-2-methylpropanesulfonic acid AN: Acrylonitrile HEMA: 2-Hydroxyethyl Methacrylate VP: N-vinyl-2-pyrrolidone APS: Ammonium Persulfate V-601: 2,2'-azobis(dimethyl isobutyrate) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) LSH: Lauryl Mercaptan ABS: Sodium dodecylbenzene sulfonate (soft type) (NEOPELEX G-15, manufactured by Kao Corporation, solid content concentration 16%) AES: ammonium polyoxyalkylene alkyl ether sulfate (ELEMINOL CLS-20, manufactured by Sanyo Chemical Industries, Ltd., solid content concentration 100%) MEK: Methyl Ethyl Ketone IPA: Isopropyl alcohol TEA: triethanolamine [Table 2]

[0149] [Table 3]

[0150] [Table 4]

[0151] <Examples 1 to 33, Comparative Examples 1 to 9> A neutralizing agent was added to the oil proofing agent composition as necessary to adjust the neutralization degree described in the table, and the composition was treated by size press.

[0152] [Table 5]

[0153] By setting the content of the neutralized acidic functional groups in the polymer to the range specified in the present invention, excellent oil resistance and air permeability can be obtained. Furthermore, when a cationic wet paper strength enhancer is added to the base paper, a tendency is observed to improve the oil resistance compared with the base paper without the addition, probably due to ionic adsorption. In addition, surprisingly, it is believed that the base paper without the addition of the agent is usually anionic, and from the viewpoint of ionic adsorption, a cationic oil-resistant agent is preferred. It is clear that by setting the content of the neutralized acidic functional groups in the polymer to the range specified in the present invention, the oil resistance of such base paper is also improved.

[0154] [Table 6]

[0155] [Table 7]

[0156] [Table 8]

[0157] By setting it to the prescribed range of the present invention, excellent oil resistance and air permeability can be obtained. In addition, from the results of Example 33 and Comparative Example 9, it can be seen that the invention disclosed in Patent Document 3 cannot obtain sufficient oil resistance. In the case where the nonionic functional group of the copolymer containing structural units derived from an unsaturated monomer having a hydrocarbon group with 1 to 60 carbon atoms, an unsaturated monomer having an acidic functional group, and an unsaturated monomer having a nonionic functional group is a hydroxyl group, it is important to control the mass ratio of the unsaturated monomer having a hydroxyl group as a nonionic functional group to the unsaturated monomer having an acidic functional group (unsaturated monomer having a hydroxyl group / unsaturated monomer having an acidic functional group) to be less than 2.6. It should be noted that, with respect to the above mass ratio, Example 33 is 2.6, and Comparative Example 9 is 3.0. In addition, the embodiment disclosed in Patent Document 3 is 2.67 or more.

[0158] The water resistance of Examples 8 and 18 was evaluated. The Stockigt sizing degrees of the base paper B were 2 seconds and 11 seconds, respectively. By controlling the chain length of the hydrocarbon group, the water resistance can be adjusted while maintaining the oil resistance and air permeability.

[0159] ·Method for producing non-fluorine-based oil resistant composition <Production Example 24> Stearic acid (1.0 part), 48% sodium hydroxide aqueous solution (0.3 part), ethanol (50.0 parts) and ion exchange water (48.7 parts) were added to a reaction container, heated under reflux until no solid was visually confirmed, and cooled to 40° C. to obtain a dispersion.

[0160] <Production Example 25> Phoslex A-18 (1.0 part, manufactured by SC Organic Chemicals, acid stearyl phosphate: Mw 437 (average value)) and 4.8% sodium hydroxide aqueous solution (3.2 parts) and ion exchange water (75.8 parts) were added, and the mixture was heated to reflux until no solid was visually confirmed. Then, the mixture was cooled to 40°C, and ethanol (20 parts) was added to obtain a dispersion. It should be noted that acid stearyl phosphate is a mixture of a monoester (Mw 350.47) and a diester (Mw 602.95), and the diester is within the prescribed range of the present invention.

[0161] <Examples 34 and 35> Table 9 shows the results of bar coating of Production Examples 24 and 25, which are oil-proofing compositions containing a low molecular weight compound, on a paper substrate.

[0162] [Table 9]

[0163] The "Joncryl PDX-7326 (manufactured by BASF, non-volatile content 38.5%)" disclosed in Patent Document 4 is compared with the present invention.

[0164] [Table 10]

[0165] The present invention is excellent in oil resistance and air permeability, but the oil repellent described in Patent Document 4 is difficult to achieve both.

[0166] Industrial Applicability By using the non-fluorine-based oil repellent composition of the present invention, oil-resistant articles can be provided.

[0167] The oil-resistant paper of the present invention is useful as a food packaging container, food packaging paper, food paper liner, and the like.

Claims

1. A non-fluorine-based oil resistant agent composition, characterized in that: A non-fluorine compound comprising a hydrocarbon group having 1 to 60 carbon atoms and a neutralized acidic functional group in at least one structural unit, and The neutralized acidic functional groups of the non-fluorine-containing compound account for 0.4 to 21% by mass. When the non-fluorine-based compound is a copolymer comprising structural units derived from an unsaturated monomer having a hydrocarbon group having 1 to 60 carbon atoms, an unsaturated monomer having an acidic functional group and an unsaturated monomer having a nonionic functional group, and the unsaturated monomer having a nonionic functional group is an unsaturated monomer having a hydroxyl group as a nonionic functional group, the mass ratio of the unsaturated monomer having a hydroxyl group to the unsaturated monomer having an acidic functional group, that is, the unsaturated monomer having a hydroxyl group / the unsaturated monomer having an acidic functional group, is less than 2.

6.

2. The non-fluorine-based oil resistant composition according to claim 1, wherein The non-fluorine-based compound includes a structure derived from the unsaturated monomer having a hydrocarbon group having 1 to 60 carbon atoms and the unsaturated monomer having an acidic functional group.

3. The non-fluorine-based oil resistant composition according to claim 1 or 2, wherein: The non-fluorine-based compound further includes a structure derived from the unsaturated monomer having a nonionic functional group.

4. The non-fluorine-based oil resistant composition according to claim 3, wherein The nonionic functional group is at least one selected from the group consisting of a hydroxyl group, a phenolic hydroxyl group, a nitrile group, an amide group, a (thio)urethane group, a (thio)urea group, a (thio)carbonate group, and an ester group.

5. The non-fluorine-based oil resistant agent composition according to claim 1 or 2, wherein: The non-fluorine-based oil resistant agent composition is used for paper.

6. The non-fluorine-based oil resistant composition according to claim 1 or 2, wherein: The non-fluorine-based oil-resistant agent composition is used for food contact purposes.

7. An oil-resistant product, characterized in that: The non-fluorine compound according to claim 1 or 2 is present on at least one of the surface and the interior of the substrate.

8. An oil-resistant paper, characterized in that: Containing the non-fluorine compound described in claim 1 or 2, The Kit value of the flat surface of the oil-proof paper measured according to TAPPI UM-557 is 1 to 6.

9. The oil-resistant paper according to claim 8, wherein: The Gurley air permeability of the oil-resistant paper measured according to the provisions of JIS P 8117:2009 is 1000 seconds or less.

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