Water-based oil-resistant agent, oil-resistant paper

Abstract

To provide a water-based oil resistant agent that gives oil resistant paper with excellent oil resistance and air permeability.SOLUTION: A water-based oil resistant agent includes: one or more resins (A) selected from the group consisting of the following (A1) and (A2); and paraffin wax (B), wherein (A1) is olefin-based resin which is a polymer containing monoolefins (a1-1) and α,β-unsaturated carboxylic acid (a1-2) of total carbon number 4 or more as essential reaction components, and (A2) is urethane resin which is a polymer containing polyol (a2-1), polyisocyanate (a2-2) and chain extender (a2-3) as essential reaction components.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a water-based oil-proofing agent and an oil-proof paper. [Background technology]

[0002] Greaseproof paper is widely used as packaging paper for cooked foods that contain a lot of oil and water, such as fried chicken, hamburgers, and grilled fish, and foods that contain a lot of fat and oil, such as chocolate, paper coverings for packaging containers and food trays, packaging paper for desiccants and oxygen absorbers, bags for pet food, heavy-duty bags for flour milling, building material paper, etc. Chemicals that impart oil resistance to paper are called greaseproofing agents.

[0003] As oil-proofing agents, fluororesin-based ones have been used conventionally, and for example, a method of coating a fluororesin-based oil-proofing agent on the surface of a paper base material, or impregnating the paper base material with the fluororesin-based oil-proofing agent, or adding the fluororesin-based oil-proofing agent to a pulp slurry, etc. However, the grease-resistant paper obtained using such an oil-proofing agent may generate perfluoro compounds when heated, which is undesirable from the viewpoint of environmental load, and in recent years, there has been a demand for oil-proofing agents that do not contain fluororesin-based resins (non-fluororesin-based oil-proofing agents).

[0004] As such an oil-proofing technology, for example, greaseproof paper having an oil-proofing layer containing starch containing hydrophobic groups and wax is known (Patent Document 1). However, in the case of non-fluorine-based oil-proofing agents, the amount of the oil-proofing agent is large in order to exhibit oil resistance while preventing the oozing of oil and fat components. This increases the oil resistance, but also leads to insufficient breathability (increased air resistance), which is likely to lead to a decrease in the flavor and storage stability of food. Although the breathability is improved in Patent Document 1, there is still room for further improvement. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2013-237941 A Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a water-based oil-proofing agent which gives an oil-proof paper having excellent oil resistance and air permeability. [Means for solving the problem]

[0007] The present inventors have conducted extensive research and found that a water-based oil-proofing agent containing a specific resin and paraffin wax can solve the above problems, and have completed the present invention. That is, the present invention relates to the following water-based oil-proofing agent and grease-resistant paper.

[0008] 1. A water-based oil-resistant agent comprising one or more resins (A) selected from the group consisting of (A1) and (A2) below, and paraffin wax (B). (A1) An olefin resin which is a polymer having as essential reactants monoolefins (a1-1) having a total carbon number of 4 or more and α,β-unsaturated carboxylic acids (a1-2). (A2) A urethane resin, which is a polymer having polyol (a2-1), polyisocyanate (a2-2) and chain extender (a2-3) as essential reaction components.

[0009] 2. The aqueous oil-resistant agent according to item 1 above, wherein the component (a1-1) is a monoolefin (I) having a total of 4 to 10 carbon atoms and a monoolefin (II) having a total of 12 to 20 carbon atoms.

[0010] 3. The water-based oil-resistant agent according to the above item 1 or 2, wherein the reactive components constituting the resin (A1) further contain an α,β-unsaturated monocarboxylic acid alkyl ester (a1-3).

[0011] 4. The water-based oil-resistant agent according to any one of items 1 to 3 above, wherein the component (a2-3) contains a dialkanolalkanoic acid.

[0012] 5. The water-based oil-resistant agent according to any one of items 1 to 4 above, wherein the content ratio of the components (A) and (B) in terms of non-volatile matter weight is (A) / (B)=10 / 90 to 90 / 10.

[0013] 6. Grease-resistant paper obtained by coating a base paper with the aqueous oil-resistant agent according to any one of items 1 to 5 above. Effect of the Invention

[0014] The aqueous oil-resistant agent of the present invention provides an oil-resistant paper having excellent oil resistance and breathability. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] The water-based oil-resistant agent of the present invention contains one or more resins (A) selected from the group consisting of specific olefin-based resins (A1) and urethane-based resins (A2), and paraffin wax (B).

[0016] First, the olefin resin (A1) (hereinafter referred to as resin (A1)) will be described.

[0017] Resin (A1) is a polymer having, as essential reaction components, monoolefins (a1-1) (hereinafter referred to as component (a1-1)) having a total carbon number of 4 or more and α,β-unsaturated carboxylic acid (a1-2) (hereinafter referred to as component (a1-2)), and is a component that imparts excellent oil resistance to the coating film of the aqueous oil-resistant agent.

[0018] The component (a1-1) is a monoolefin having a total carbon number of 4 or more.

[0019] Examples of the component (a1-1) include 1-butene, 2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, 3-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 2-octene, 3-octene, 4-octene, isooctene, 1-decene, 2-decene, 3-decene, 4-decene, 1-dodecene, 2-dodecene, 3-dodecene, 1-tetradecene, 2-tetradecene, 3 ... Linear olefins such as tetradecene, 3-tetradecene, 1-hexadecene, 2-hexadecene, 3-hexadecene, 1-octadecene, 2-octadecene, 3-octadecene, 1-eicosene, 1-tetracosene, and 1-triacontene; 2-methylpropene (isobutene), 2,4,4-trimethyl-1-pentene, 2,4,4-trimethyl-2-pentene, and 2,4,4-trimethyl-1-pentene. Mixtures with 2,4,4-trimethyl-2-pentene (also called diisobutylene), 2-methyl-1-butene, 3-methyl-1-butene (isopentene), 2-methyl-1-pentene, 2-ethyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene (isohexene), 2-ethyl-1-pentene, 3-ethyl-1-pentene, 2-methyl-3-ethyl-1-pentene, 2-methyl-1-hexene, 3-methyl-1-hexene, 4-methyl-1-hexene, 2-ethyl-1-hexene, 3-ethyl-1-hexene, 2-methyl-1-octene, 3-methyl-1-octene, branched olefins such as cyclohexene, methylcyclohexene, vinylcyclohexane, 4-vinylcyclohexene, cyclopentene, methylcyclopentene, etc. These may be used alone or in combination of two or more. In addition, isomers (cis and trans isomers) of these olefins can also be used without any particular limitations. Among them, monoolefins having a total carbon number of 4 to 20 are preferred, and from the viewpoints that the oil-proofing agent obtained from the balance of hydrophilicity / hydrophobicity is water-soluble and exhibits excellent oil resistance, it is more preferred to combine monoolefins having a total carbon number of 4 to 10 and monoolefins having a total carbon number of 12 to 20, and even more preferred to combine monoolefins having a total carbon number of 6 to 8 and monoolefins having a total carbon number of 15 to 20.

[0020] The amount of component (a1-1) used is usually 20 to 70% by weight, and preferably 30 to 60% by weight, based on the non-volatile weight of all reactive components constituting resin (A1), taken as 100% by weight (the same applies below).

[0021] The component (a1-2) is an α,β-unsaturated carboxylic acid.

[0022] Examples of the (a1-2) component include α,β-unsaturated dicarboxylic acids such as maleic acid, itaconic acid, fumaric acid, muconic acid, and citraconic acid; α,β-unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; acid anhydrides of the above unsaturated dicarboxylic acids, acid anhydrides of the above unsaturated monocarboxylic acids, monoalkyl esters of the above unsaturated dicarboxylic acids, and monoalkyl amides of the above unsaturated dicarboxylic acids.

[0023] Examples of the alkyl group of the monoalkyl ester and the monoalkyl amide include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a s-butyl group, a t-butyl group, an n-pentyl group, an isopentyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group, a (2-ethylhexyl) group, an n-decyl group, an n-dodecyl group, an n-tetradecyl group, an n-hexadecyl group, an n-octadecyl group, an n-nonadecyl group, an n-eicosyl group, and an n-docosyl group.

[0024] These (a1-2) components may be used alone or in combination of two or more. Among them, maleic acid, fumaric acid, itaconic acid, maleic anhydride, and (meth)acrylic acid are preferred from the viewpoint of making the polymer produced during the reaction more soluble or dispersible in water.

[0025] As the component (a1-2), a neutralized salt of these α,β-unsaturated carboxylic acids may be used. Examples of the neutralized salt include alkali metal salts such as sodium salts and potassium salts, and ammonium salts.

[0026] When preparing the neutralized salt, for example, hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, inorganic amines such as ammonia and ammonium carbonate, alkyl amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine and n-butylamine, cycloalkyl amines such as cyclohexylamine, aromatic amines such as aniline, etc. can be used alone or in combination of two or more of them.

[0027] The amount of the component (a1-2) used is usually 10 to 50% by weight, and preferably 20 to 40% by weight, based on 100% by weight of all the reactive components constituting the resin (A1).

[0028] The reactive components constituting the resin (A1) may further contain an α,β-unsaturated monocarboxylic acid alkyl ester (a1-3) (hereinafter referred to as the (a1-3) component).

[0029] Examples of α,β-unsaturated monocarboxylic acids include those described in the previous paragraph. These may be used alone or in combination of two or more. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, and n-docosyl. These may be used alone or in combination of two or more.

[0030] The amount of the component (a1-3) used is usually 20% by weight or less, and preferably 1 to 10% by weight, based on 100% by weight of all the reactive components constituting the resin (A1).

[0031] The reactive components constituting the resin (A1) may contain a polymerizable monomer (a1-4) (hereinafter referred to as component (a1-4)) other than the components (a1-1) to (a1-3).

[0032] Examples of the component (a1-4) include styrenes such as styrene, α-methylstyrene, t-butylstyrene, dimethylstyrene, acetoxystyrene, hydroxystyrene, vinyltoluene, and chlorovinyltoluene; 2-Hydroxymethyl (meth)acrylate, 2-Hydroxyethyl (meth)acrylate 、 (meth)acrylic acid esters having a hydroxy group, such as 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, glycerin mono(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol mono(meth)acrylate, and pentaerythritol di(meth)acrylate; aminoalkyl (meth)acrylates such as aminoethyl (meth)acrylate, aminopropyl (meth)acrylate, aminobutyl (meth)acrylate, N-methylaminoethyl (meth)acrylate, N-methylaminopropyl (meth)acrylate, N-methylaminobutyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-dimethylaminobutyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate, and N,N-diethylaminobutyl (meth)acrylate; Monomers having a sulfo group, such as styrene sulfonic acid, α-methylstyrene sulfonic acid, vinyl sulfonic acid, 2-(meth)acrylamido-2-methylpropanesulfonic acid, (meth)allylamido-N-methylsulfonic acid, (meth)acrylamidophenylpropanesulfonic acid, (meth)allylsulfonic acid, (meth)acrylate sulfoethyl, (meth)acrylate sulfopropyl, and (meth)acrylate sulfo 2-hydroxypropyl; Divinyl esters such as divinyl adipate and divinyl sebacate; polyethylene glycol mono(meth)acrylates such as diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, and tetraethylene glycol mono(meth)acrylate; Polyethylene glycol di(meth)acrylates such as ethylene glycol di(meth)acrylate and diethylene glycol di(meth)acrylate; polyalkylene glycol mono(meth)acrylates such as polypropylene glycol mono(meth)acrylate, methoxypolyethylene glycol mono(meth)acrylate, polytrimethylene glycol mono(meth)acrylate, polytetramethylene glycol mono(meth)acrylate and polyethylene glycol propylene glycol mono(meth)acrylate; (meth)acrylamides such as (meth)acrylamide, N-methylol (meth)acrylamide, N-ethyl (meth)acrylamide, N-isopropylacrylamide, N-butyl (meth)acrylamide, N-octyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N-propoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, N-2-hydroxyethyl (meth)acrylamide, N,N-dihydroxyethyl (meth)acrylamide, N-(1,1-dimethyl-3-oxobutyl)acrylamide, N-allyl (meth)acrylamide, (meth)acrylamidoglycolic acid, 2-acrylamido-2-methylpropanesulfonic acid, N,N-dimethylacrylamide, N,N-diethylacrylamide, N,N-diallyl (meth)acrylamide, N,N'-methylenebis (meth)acrylamide, and N,N'-ethylenebis (meth)acrylamide; Aromatic polyvinyls such as divinylbenzene, 1,3,5-triacryloylhexahydro-1,3,5-triazine, triallyl isocyanurate, triallyl trimellitate, triallylamine, tetramethylolmethane tetraacrylate, and tetraallyl pyromellitate; These may be used alone or in combination of two or more.

[0033] The amount of the component (a1-4) used is usually 10% by weight or less, and preferably 5% by weight or less, based on 100% by weight of all the reactive components constituting the resin (A1).

[0034] Resin (A1) can be obtained by charging components (a1-1) and (a1-2), and, if necessary, components (a1-3) and (a1-4), adding a solvent, and reacting them in the presence of a polymerization initiator.

[0035] Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, ethylbenzene, n-propylbenzene, t-butylbenzene, o-xylene, m-xylene, p-xylene, tetralin, decalin, and aromatic naphtha; esters such as ethyl acetate, n-butyl acetate, n-amyl acetate, 2-hydroxyethyl acetate, 2-butoxyethyl acetate, 3-methoxybutyl acetate, and methyl benzoate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone, and methylcyclohexanone; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, s-butanol, and t-butanol; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; and water such as ion-exchanged water, purified water, tap water, soft water, hard water, and industrial water. These may be used alone or in combination of two or more. These solvents may be added during the reaction. Furthermore, when a solvent other than water is used, it is preferable to finally remove the solvent from the reaction system by vacuum distillation or the like.

[0036] The amount of the solvent used is preferably adjusted so that the reaction concentration is 10 to 80% by weight.

[0037] Examples of the polymerization initiator include persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate; azo compounds such as 2,2'-azobis(2-amidinopropane) hydrochloride, 2,2'-azobis[2(2-imidazolin-2-yl)propane] hydrochloride, 2,2'-azobisisobutyronitrile, and dimethyl-2,2'-azobisisobutyrate; organic peroxides such as benzoyl peroxide, dicumyl peroxide, and lauryl peroxide; and hydrogen peroxide. These may be used alone or in combination of two or more. In addition, a reducing agent such as sodium sulfite or sodium thiosulfate may be used in combination with the polymerization initiator, and the reaction system may be a redox system.

[0038] The amount of the polymerization initiator used is usually about 0.01 to 5 parts by weight, and preferably about 0.05 to 3 parts by weight, per 100 parts by weight of all the reaction components constituting the resin (A1).

[0039] The reaction conditions include, for example, a reaction temperature of usually 40 to 150° C., and preferably 60 to 120° C., and a reaction time of usually 1 to 10 hours, and preferably 1 to 3 hours.

[0040] A chain transfer agent may be further added to the reaction. Examples of the chain transfer agent include alkyl mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, and n-octadecyl mercaptan; 2-mercaptobenzothiazole, bromotrichloromethane, and α-methylstyrene dimer. These may be used alone or in combination of two or more.

[0041] The amount of the chain transfer agent used is usually 5 parts by weight or less, and preferably 3 parts by weight or less, per 100 parts by weight of all the reaction components constituting the resin (A1).

[0042] In the above reaction, the component (B) described below may be added before or during the reaction.

[0043] In the reaction, inorganic acids such as sulfuric acid and phosphoric acid, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, inorganic amines such as ammonia and ammonium carbonate, alkyl amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine and n-butylamine, cycloalkyl amines such as cyclohexylamine, aromatic amines such as aniline, etc. may be added before, during, or after the reaction, as necessary. The reaction system is preferably kept under a nitrogen atmosphere.

[0044] Obtained Resin (A1 ) The composition may contain additives such as pigments, water retention agents, antifoaming agents, preservatives, leveling agents, colorants, antiblocking agents, antioxidants, UV absorbers, thickeners, dispersants, and fillers.

[0045] Regarding physical properties of the obtained resin (A1), for example, the weight average molecular weight is usually about 1,000 to 500,000, and preferably 5,000 to 50,000. The "weight average molecular weight" here is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

[0046] The viscosity of a solution of resin (A1) having a non-volatile content of 20% by weight at a temperature of 25° C. is usually 5 to 50,000 mPa s, and preferably 10 to 10,000 mPa s. The “viscosity” here refers to a value measured with a B-type viscometer.

[0047] Furthermore, the pH of the resin (A1) is usually 5 to 11, and preferably 6 to 10. The "pH" here refers to a value measured with a commercially available pH measuring device.

[0048] Next, the urethane resin (A2) (hereinafter referred to as resin (A2)) will be described.

[0049] Resin (A2) is a polymer having polyol (a2-1) (hereinafter referred to as component (a2-1)), polyisocyanate (a2-2) (hereinafter referred to as component (a2-2)), and chain extender (a2-3) (hereinafter referred to as component (a2-3)) as essential reaction components. Tie This component gives the oil-resistant coating excellent oil resistance.

[0050] The component (a2-1) is a compound having two or more hydroxyl groups in the molecule, and examples thereof include polyether polyol, poly(meth)acrylic polyol, polycaprolactone polyol, polycarbonate polyol, etc. These may be used alone or in combination of two or more. Among them, polyether polyol is preferred.

[0051] Examples of polyether polyols include polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polydecamethylene glycol, polyoxyethylene-polyoxypropylene glycol, polyoxytetramethylene-polyoxyethylene glycol, polyoxytetramethylene-polyoxypropylene glycol, etc. The polyether polyol may have a random structure or a block structure.

[0052] Commercially available polyether polyols include ADEKA Polyether P-400, ADEKA Polyether G-400, ADEKA Polyether T-400, ADEKA Polyether AM-302, ADEKA Polyether P1000, and ADEKA Polyether P2000 (all manufactured by ADEKA Corporation); Polyethylene Glycol #1,540 (manufactured by Nacalai Tesque, Inc.); Dipropylene Glycol and Polypropylene Glycol 400 (manufactured by Junsei Chemical Co., Ltd.); PEG #200, PEG #300, PEG #400, PEG #600, PEG #1000, and PEG #1500. Examples include "PEG#2000", "PEG#4000", "Uniol D-200", "Uniol D-700", "Uniol D-1000", "Uniol D-1200", "Uniol D-2000", "Uniol D-4000", "Uniol PB-500", "Uniol PB-700", "Uniol PB-1000", "Uniol PB-2000", "Polyserine DC-1100", "Polyserine DC-1800E", "Polyserine DC-3000E", "Polyserine DCB-1000", "Polyserine DCB-2000", and "Polyserine DCB-4000" (all manufactured by NOF Corporation).

[0053] Examples of the component (a2-2) include aliphatic diisocyanates such as methylene diisocyanate, isopropylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and dimer diisocyanate in which the carboxyl groups of a dimer acid are substituted with isocyanate groups; Alicyclic diisocyanates such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-di(isocyanatemethyl)cyclohexane, and methylcyclohexane diisocyanate; Aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-diphenyltetramethylmethane diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, 1,5-naphthylene diisocyanate, 4,4'-dibenzyl isocyanate, and 1,3-phenylene diisocyanate; and amino acid diisocyanates such as lysine diisocyanate. These may be used alone or in combination of two or more. Furthermore, as the resin (A2), nurates, adducts or biuret forms of these may be used.

[0054] The ratio of the (a2-1) component and the (a2-2) component used is usually determined by the number of moles of isocyanate groups (NCO (a2-2) ) and the number of moles of hydroxyl groups in the (a2-1) component (OH (a2-1) ) and the ratio (NCO (a2-2) / OH (a2-1) ) is preferably about 1.1 / 1 to 8 / 1.

[0055] The component (a2-3) is a chain extender.

[0056] Examples of the component (a2-3) include ethylenediamine, propylenediamine, and hexamethylenediamine. 、 Diamines such as isophoronediamine, dimer diamine, dicyclohexylmethane-4,4'-diamine, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, and di-2-hydroxypropylethylenediamine; Triamines such as diethylenetriamine, dipropylenetriamine, and dibutylenetriamine; Tetramines such as triethylenetetramine and tripropylenetetramine; N-alkyldialkanolamines such as N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-isopropyldiethanolamine, N-butyldiethanolamine, N-isobutyldiethanolamine, N-oleyldiethanolamine, N-stearyldiethanolamine, N-methyldiisopropanolamine, N-ethyldiisopropanolamine, N-propyldiisopropanolamine, and N-butyldiisopropanolamine; Hydrazine or its hydrazine derivatives (such as adipic acid hydrazide); Dialkanolalkanoic acids such as glyceric acid, dioxymaleic acid, dioxyfumaric acid, dimethylolacetic acid, dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolpentanoic acid, and dimethylolhexanoic acid; Examples of the aromatic hydroxycarboxylic acids include 4,4-di(hydroxyphenyl)butanoic acid, 4,4-di(hydroxyphenyl)pentanoic acid, and 2,6-dioxybenzoic acid. These may be used alone or in combination of two or more. Among them, dialkanolalkanoic acids are preferred from the viewpoint of making the resulting polymer more soluble or dispersible in water.

[0057] The dialkanolamine may be used in the form of a quaternary salt. The quaternary salt refers to a product of the dialkanolamine reacting with a quaternizing agent, and examples of the quaternizing agent include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as dimethyl sulfate, acetic acid, and propionic acid; and organic halogens such as methyl chloride, benzyl chloride, and epichlorohydrin.

[0058] The carboxyl groups of the dialkanolalkanoic acids and aromatic hydroxycarboxylic acids may be neutralized with a neutralizing agent.

[0059] Examples of the neutralizing agent include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, ammonia, and organic amines such as trimethylamine, triethylamine, triethanolamine, triisopropanolamine, N,N-dimethylethanolamine, and N,N-diethylethanolamine. These may be used alone or in combination of two or more.

[0060] The amount of the component (a2-3) used is usually 1 to 30% by weight, and preferably 3 to 20% by weight, based on 100% by weight of the reactive components constituting the resin (A2).

[0061] The resin (A2) of the present invention may contain a hydroxyalkyl (meth)acrylate ester (a2-4) (hereinafter referred to as component (a2-4)) as a reactive component.

[0062] Examples of the (a2-4) component include 2-hydroxyethyl (meth)acrylate, 2-hydroxy n-propyl (meth)acrylate, 3-hydroxy n-propyl (meth)acrylate, 3-hydroxy n-butyl (meth)acrylate, 4-hydroxy n-butyl (meth)acrylate, 6-hydroxy n-hexyl (meth)acrylate, etc. These may be used alone or in combination of two or more.

[0063] The amount of the component (a2-4) used is usually 10% by weight or less, and preferably 5% by weight or less, based on 100% by weight of the reactive components constituting the resin (A2).

[0064] When the component (a2-4) is used, it may be further reacted with a (meth)acrylic acid monoalkyl ester (a2-5) having no hydroxyl group (hereinafter referred to as component (a2-5)).

[0065] Examples of the (a2-5) component include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, myristyl (meth)acrylate, isomyristyl (meth)acrylate, palmityl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, etc. These may be used alone or in combination of two or more.

[0066] The amount of the component (a2-5) used is usually 50% by weight or less, and preferably 30% by weight or less, based on 100% by weight of the reactive components constituting the resin (A2).

[0067] The reaction components may further contain a chain extension terminator (a2-6) (hereinafter referred to as component (a2-6)). Examples of component (a2-6) include monoalcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, and isobutyl alcohol; monoamines such as ethylamine, n-propylamine, diethylamine, di-n-propylamine, and di-n-butylamine; and alkanol monoamines such as monoethanolamine and diethanolamine. These may be used alone or in combination of two or more.

[0068] The amount of the component (a2-6) used is usually 5% by weight or less, and preferably 3% by weight or less, based on 100% by weight of the reactive components constituting the resin (A2).

[0069] Resin (A2) can be obtained, for example, by reacting component (a2-1) with component (a2-2) to produce a urethane prepolymer, and then reacting the urethane prepolymer with component (a2-3) and, if necessary, with components (a2-4) to (a2-6).

[0070] As for reaction conditions for the step of obtaining the urethane prepolymer, the temperature is usually about 40 to 150° C., and preferably about 60 to 100° C., and the time is usually about 1 to 20 hours, and preferably about 1 to 10 hours. Next, the urethane prepolymer is reacted with component (a2-3), and optionally components (a2-4) to (a2-6), under conditions such as a temperature of usually about 20 to 100° C., and preferably about 30 to 80° C., and a time of usually about 1 to 10 hours, and preferably about 1 to 5 hours. The method and order of mixing the components are not particularly limited.

[0071] The production of these resins (A2) may be carried out in the absence of a solvent or in the presence of a solvent.

[0072] Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, ethylbenzene, n-propylbenzene, t-butylbenzene, o-xylene, m-xylene, p-xylene, tetralin, decalin, and aromatic naphtha; aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane, isooctane, and n-decane; alicyclic hydrocarbons such as cyclohexane; esters such as ethyl acetate, n-butyl acetate, n-amyl acetate, 2-hydroxyethyl acetate, 2-butoxyethyl acetate, 3-methoxybutyl acetate, and methyl benzoate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone, and methylcyclohexanone; Examples of the solvent include glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, s-butanol, and t-butanol; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; amines such as N-methylpyrrolidone; water such as ion-exchanged water, purified water, tap water, soft water, hard water, and industrial water; and dimethyl sulfoxide. These may be used alone or in combination of two or more. After the reaction is completed, the solvent may be distilled off under reduced pressure or the like.

[0073] The amount of the solvent used is preferably adjusted so that the reaction concentration is 10% by weight or more.

[0074] In the above reaction, the component (B) described below may be added.

[0075] The resin (A2) may further contain pigments, water retention agents, antifoaming agents, preservatives, leveling agents, colorants, antiblocking agents, antioxidants, UV absorbers, thickeners, dispersants, fillers, and the like.

[0076] The weight average molecular weight of the obtained resin (A2) is 5,000 to 500,000. The weight average molecular weight is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

[0077] The viscosity of a solution of resin (A2) having a non-volatile content of 35% by weight at a temperature of 25° C. is usually 5 to 20,000 mPa s, and preferably 10 to 10,000 mPa s. The “viscosity” here refers to a value measured with a B-type viscometer.

[0078] Component (B) is paraffin wax and water Tie This component gives the oil-resistant coating excellent oil resistance.

[0079] Paraffin wax is produced by vacuum distilling crude oil, and is obtained by separating and refining highly crystalline hydrocarbons from the distillate obtained. It is composed mainly of straight-chain hydrocarbons (normal paraffins).

[0080] Regarding physical properties of the component (B), for example, the melting point is preferably 45 to 80°C, and more preferably 55 to 80°C.

[0081] In the present invention, it is preferable to use the component (B) in an aqueous emulsion prepared by using a dispersant. Examples of the dispersant include nonionic surfactants, cationic surfactants, and anionic surfactants described in JP-A-2013-237941.

[0082] Commercially available products of component (B) include, in the form of solids, for example, "Paraffin 115", "Paraffin 120", "Paraffin 125", "Paraffin 130", "Paraffin 135", "Paraffin 140", "Paraffin 145", "Paraffin 150", "Paraffin 155", and "HNP-51" (all manufactured by Nippon Seiro Co., Ltd.). In addition, in the form of aqueous emulsions, for example, "Sizepine W-116H" (manufactured by Arakawa Chemical Industries, Ltd.) can be used. These may be used alone or in combination of two or more kinds.

[0083] The non-volatile weight ratio of component (A) to component (B) is: water Tie In order for the coating of the oil-resistant agent to exhibit excellent oil resistance, (A) / (B) is preferably 10 / 90 to 90 / 10, and more preferably 20 / 80 to 80 / 20.

[0084] The water-based oil-resistant agent of the present invention is obtained by mixing components (A) and (B), and water as necessary. The mixing conditions are, for example, a temperature of 10 to 90° C. (preferably 20 to 80° C.). The mixing order, mixing method, and mixing time of each component are not particularly limited.

[0085] The water-based oil-resistant agent of the present invention may further contain additives such as pigments, water retention agents, antifoaming agents, antioxidants, preservatives, leveling agents, and colorants.

[0086] As for the physical properties of the resulting water-based oil-resistant agent, the non-volatile content is usually 5 to 50% by weight, and preferably 10 to 40% by weight.

[0087] The viscosity of a solution of the water-based oil-resistant agent having a non-volatile content of 10% by weight at a temperature of 25° C. is usually 5 to 100 mPa·s, and preferably 10 to 80 mPa·s.

[0088] The grease-resistant paper of the present invention is obtained by coating the aqueous grease-resistant agent on a base paper.

[0089] Examples of base paper include chemical pulps such as hardwood pulp (LBKP) and softwood pulp (NBKP); mechanical pulps such as groundwood pulp (GP), refiner ground pulp (RGP), and thermomechanical pulp (TMP); and paper made by various papermaking machines using DIP, mercerized pulp, waste paper pulp, etc., and more specifically, bleached kraft paper, unbleached kraft paper, fine paper, medium quality paper, lightly coated paper, coated paper, processed base paper, paperboard, white paperboard, liner, semi-glassine paper, glassine paper, parchment paper, etc. In addition, the pulp may contain pH adjusters such as aluminum sulfate, sulfuric acid, and sodium hydroxide; papermaking chemicals such as sizing agents, paper strength enhancers such as starch and polyacrylamide, and wet strength agents; and fillers such as talc, clay, kaolin, titanium dioxide, and calcium carbonate.

[0090] Examples of methods for applying the water-based oil-resistant agent include a bar coater, a knife coater, a size press coater, a roll coater, a reverse roll coater, a curtain coater, a gravure coater, an air knife coater, a calendar, a gate roll coater, a blade coater, a two-roll size press, and a rod metering. The amount of the coating liquid applied (based on non-volatile content) is not particularly limited, but is usually 0.1 to 10 g / m. 2 Approximately, preferably 1 to 6 g / m 2 That's about it.

[0091] After coating, the base paper is dried with heat. Examples of heat sources include hot air dryers, infrared heaters, rotary dryers, etc. The drying conditions are, for example, a temperature of 80 to 180°C (preferably 100 to 150°C) and a time of 0.1 to 180 minutes (preferably 0.5 to 60 minutes). EXAMPLES

[0092] The present invention will be described below with reference to examples, but the present invention is not limited thereto. In the examples and comparative examples, "parts" and "%" are by weight unless otherwise specified.

[0093] Manufacturing Example 1 While introducing nitrogen into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and two dropping funnels, 98 parts of maleic anhydride and 75.2 parts of toluene were charged, and the reaction system was heated to 110°C while stirring under a nitrogen stream. Next, 73.7 parts of diisobutylene (2,2,4-trimethyl-1-pentene content 76%), 112 parts of 1-hexadecene, and 12 parts of n-butyl acrylate were charged into the dropping funnel (1), and 6.6 parts of t-butyl peroxybenzoate and 35 parts of toluene were charged into the dropping funnel (2), and each was dropped into the vessel over 1.5 hours. After keeping the temperature under reflux for 2 hours, 2.6 parts of t-butyl peroxybenzoate and 15 parts of toluene were dropped over 30 minutes, and the temperature was kept at the same temperature for another 1 hour. 16 parts of sodium hydroxide, 85 parts of 28% aqueous ammonia and a specified amount of water were added and stirred, and the toluene was distilled off under reduced pressure to obtain an olefin resin (A1-1) with a non-volatile concentration of 20%, a viscosity of 80 mPa·s and a pH of 9.0.

[0094] Manufacturing Example 2 While introducing nitrogen into a reaction vessel similar to that of Production Example 1, 98 parts of maleic acid and 75.2 parts of toluene were charged, and the reaction system was heated to 110°C while stirring under a nitrogen stream. Next, 197.7 parts of diisobutylene (content of 2,2,4-trimethyl-1-pentene: 76%) was charged into the dropping funnel (1), and 6.6 parts of t-butyl peroxybenzoate and 35 parts of toluene were charged into the dropping funnel (2), and each was dropped into the vessel over 1.5 hours. After keeping the temperature under reflux for 2 hours, 2.6 parts of t-butyl peroxybenzoate and 15 parts of toluene were dropped over 30 minutes, and the temperature was kept at the same temperature for another hour. 16 parts of sodium hydroxide, 85 parts of 28% aqueous ammonia, and a specified amount of water were added and stirred, and the toluene was distilled off under reduced pressure to obtain an olefin resin (A1-2) with a non-volatile content of 20%, a viscosity of 100 mPa·s, and a pH of 9.0.

[0095] Production Example 3 A reaction vessel equipped with a stirrer, thermometer, cooling tube, and nitrogen gas inlet tube was charged with 59.4 parts of dimethylolbutanoic acid, 489.9 parts of Polyserine DCB-2000 (polyoxytetramethylene-polyoxypropylene glycol, number average molecular weight 2000, NOF Corp.), and 200.8 parts of isophorone diisocyanate, and reacted for 5 hours at 85°C under a nitrogen stream to obtain 750 parts of urethane prepolymer. Next, the urethane prepolymer was added and dispersed under stirring in an aqueous solution consisting of 1208 parts of water, 225 parts of isopropyl alcohol, 40.5 parts of triethylamine, and 43.3 parts of adipic acid dihydrazide. The mixture was reacted for 3 hours at 50°C, and a specified amount of water was added to obtain a mixture with a non-volatile content of 35% and a viscosity of 800 mPa·s. 、 A urethane resin (A2-1) having a pH of 8.0 was obtained.

[0096] Production Example 4 In a reaction vessel equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen gas inlet tube, 59.4 parts of dimethylolbutanoic acid, 489.9 parts of PTMG1000 (polytetramethylene glycol, number average molecular weight 1000, manufactured by Mitsubishi Chemical Corporation), and 275.5 parts of isophorone diisocyanate were charged, and the mixture was reacted for 5 hours at 85°C under a nitrogen stream to obtain 824 parts of urethane prepolymer. Next, the urethane prepolymer was added and dispersed under stirring in an aqueous solution consisting of 1340 parts of water, 225 parts of isopropyl alcohol, 40.5 parts of triethylamine, and 43.3 parts of adipic acid dihydrazide. The mixture was reacted for 3 hours at 50°C, and a specified amount of water was added to obtain a urethane resin (A2-2) with a non-volatile content of 35%, a viscosity of 800 mPa·s, and a pH of 8.0.

[0097] Example 1 A water-based oil-resistant agent was obtained by mixing 250.0 parts of olefin (A1-1) (50 parts non-volatile content), 166.7 parts of paraffin wax (product name: "Sizepine W-116H", manufactured by Arakawa Chemical Industries, Ltd.) (50 parts non-volatile content), and 583.3 parts of ion-exchanged water.

[0098] Examples 2 to 7, Comparative Examples 1 to 9 The same procedure as in Example 1 was carried out except that the compositions and contents were changed as shown in Table 1, to obtain water-based oil-resistant agents.

[0099] (Preparation of greaseproof paper) Commercially available processed base paper (basis weight 50g / m 2 A water-based oil-resistant agent was applied to the paper (paper with a Stockigt sizing degree of 12 seconds and an air resistance of 80 seconds) using a wire bar of any desired size, and then the paper was dried for 5 minutes in a hot air dryer set at 120°C to obtain oil-resistant paper.

[0100] (Oil resistance) The coated surface was measured using JAPAN TAPPI Paper and Pulp Test Method No. 41:2000 (kit method). The kit oil resistance for use as oil-resistant paper is preferably grade 4 or higher, and when this value is reached, the coating amount of the water-based oil-resistant agent is 5 g / m 2 The following were considered to be good:

[0101] (Breathability) The air resistance was measured according to JIS P8117. For greaseproof paper with high air permeability, it is preferable that the air permeability is 1000 seconds or less.

[0102] [Table 1] *1: The weight parts of each component are expressed as the weight of non-volatile content.

[0103] The symbols in Table 1 represent the following compounds. (resin) A1-1: Olefin resin of Production Example 1 A1-2: Olefin resin of Production Example 2 A2-1: Urethane resin of Production Example 3 A2-2: Urethane resin of Production Example 4 C-1: Olefin resin with 2 carbon atoms (product name: Chemipearl S100, manufactured by Mitsui Chemicals, Inc.) C-2: Styrene-based resin (product name: "Polymaron 1383", manufactured by Arakawa Chemical Industries, Ltd.) C-3: Polyvinyl alcohol (product name: "Kuraray Poval 11-98", manufactured by Kuraray Co., Ltd.) (wax) B-1: Paraffin wax (product name: "Sizepine W-116H", manufactured by Arakawa Chemical Industries, Ltd.) D-1: Polyethylene wax (product name: Chemipearl W401, manufactured by Mitsui Chemicals, Inc.) D-2: AKD-based emulsion (product name: Sizepine K-924, manufactured by Arakawa Chemical Industries, Ltd.) D-3: Fatty acid emulsion (product name: Sizepine CA-956, manufactured by Arakawa Chemical Industries, Ltd.)

Claims

1. The composition comprises one or more resins (A) selected from the group consisting of the following (A1) and (A2), and paraffin wax (B), A water-based oil-resistant agent in which the content ratio of the components (A) and (B) in terms of non-volatile weight is (A) / (B)=10 / 90 to 90 / 10. (A1) An olefin resin which is a polymer having as essential reactants (a1-1) monoolefins having a total carbon number of 4 or more and (a1-2) α,β-unsaturated carboxylic acid (A2) A urethane-based resin which is a polymer having polyol (a2-1), polyisocyanate (a2-2), and chain extender (a2-3) as essential reaction components

2. 2. The aqueous oil-resistant agent according to claim 1, wherein the component (a1-1) is a monoolefin (I) having a total of 4 to 10 carbon atoms and a monoolefin (II) having a total of 12 to 20 carbon atoms.

3. 3. The water-based oil-resistant agent according to claim 1, wherein the reactive components constituting the resin (A1) further comprise an α,β-unsaturated monocarboxylic acid alkyl ester (a1-3).

4. The aqueous oil-resistant agent according to any one of claims 1 to 3, wherein the component (a2-3) comprises a dialkanolalkanoic acid.

5. An oil-resistant paper obtained by coating a base paper with the aqueous oil-resistant agent according to any one of claims 1 to 4.

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