Gravure ink composition for adsorbing ammonia-based compounds, printed matter adsorbing ammonia-based compounds, laminate, method for manufacturing printed matter adsorbing ammonia-based compounds, method for manufacturing laminate, packaging bag, packaging container

Abstract

To provide a gravure ink composition for adsorbing ammonia compounds that can reduce discomfort ammonia compound smells generated in living environments, such as raw smells of meat and seafood, their putrid smells, garbage smells, excretion smells in toilets and the like, cigarette smells, or body odors, and also enables production of a printed material having suitable printability by a simple and easy printing process.SOLUTION: A gravure ink composition for adsorbing ammonia compounds has a substrate, and an ammonia compound adsorbing layer having a thickness of 0.1-5 μm on at least one of the substrate, and is used in an ammonia compound-adsorbing printed material. The gravure ink composition for adsorbing ammonia compounds contains an acidic group-containing thermoplastic resin, and a solvent.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an ink composition that suppresses unpleasant ammonia-based compound odors that occur in living environments, such as the fishy odor of meat products such as meat and seafood, the putrid odor that occurs when these products decay, the odor of food waste, the odor of excretions in toilets, cigarette smoke, and body odor. [Background technology]

[0002] Unpleasant ammonia-based compound odors that occur in the living environment include methylamine, which causes the fishy smell of meat and seafood products, and trimethylamine, which causes the putrid odor that occurs when these products decay; indoles such as indole and skatole, which cause excrement odors in toilets; amine compounds such as pyridine, which cause cigarette smoke; and ammonia-based body odor, cigarette smoke, garbage odor, and excrement odors.

[0003] Patent Document 1 proposes a pet sheet that includes an absorbent body that has excellent absorbency for liquids and a hydrophilic top sheet placed on the absorbent body, with an acidic polymer solution fixed to the absorbent body and top sheet, and that can deodorize alkaline substances such as ammonia and trimethylamine, which cause bad odors emitted from urine.However, although it is stated that the acidic polymer solution contains sulfonic groups, carboxyl groups, and phosphate groups, the details are unclear, and there is no statement or suggestion that it contains resin.The sheet is applied by spraying, and is not produced by printing, and there is no statement or suggestion that this is the case.

[0004] Patent Document 2 proposes an odor adsorption sheet having at least a gas barrier layer and an odor adsorption layer of a single layer or a multilayer configuration having two or more layers, the odor adsorption layer being made of a heat-sealable resin, and the chemical adsorbent contained in the odor adsorption layer being at least one chemical adsorbent selected from the group consisting of compounds having a hydroxyl group, metal carbonates, metal hydrogen carbonates, amino group-containing compounds, amide group-containing compounds, phosphoric acid, sulfonic acid, carboxylic acid, metal salts of phosphoric acid, metal salts of sulfonic acid, metal salts of carboxylic acid, and metal oxides. This odor adsorption sheet is capable of efficiently adsorbing odors without desorbing the odors once adsorbed, and exhibits a high adsorption effect over a long period of time without decreasing odor adsorption capacity. However, the odor adsorbent used in the odor adsorption layer is made by supporting the chemical adsorbent on an inorganic porous material, which is kneaded into a heat-sealable resin to form a masterbatch. The lamination method is by melt extrusion, not by printing, and there is no mention or suggestion of this method. If it were to be produced by printing (e.g., gravure ink), the inorganic porous material would need to be dispersed in a resin varnish (a binder made by mixing resin and solvent, etc.), which could result in the resin varnish penetrating the numerous pores and forming a resin film, drastically reducing the odor adsorption effect. Furthermore, the thickness of the odor adsorption layer was 50 μm in the examples, which is clearly not a thickness that can be applied by printing. Furthermore, since a powder form is preferred for inorganic porous materials, there is a risk that they may fall off after being fixed.

[0005] Patent Document 3 proposes a laminate with a waterproof sheet on the backside, which is composed of a water-absorbent sheet, pulp, a water-absorbent resin, a water-absorbent sheet, and a top sheet laminated in that order on the waterproof sheet. A deodorizing antibacterial agent containing a complex of metal salt and silicate is adhered to at least one of the pulp, the water-absorbent sheet, and the top sheet. This laminate is capable of deodorizing excrement-related odors, including not only ammonia but also sulfur components, and inhibiting bacterial growth. However, since the deodorizing antibacterial agent used is a powder of a metal salt and silicate, there is a risk of it falling off after adhering. Furthermore, a comparative example using only sodium polyacrylate without the deodorizing antibacterial agent showed good results in removing ammonia and indole (Comparative Example 1). This comparative example suggests that sodium polyacrylate has a certain effect on removing ammonia and indole, but the example simply uses particulate sodium polyacrylate as the water-absorbent resin and disperses it, without suggesting or describing its use in printing. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2002-010718 [Patent Document 2] Japanese Patent Application Publication No. 2018-199527 [Patent Document 3] Japanese Patent Application Publication No. 2019-014131 Summary of the Invention [Problem to be solved by the invention]

[0007] That is, the present invention is (1) A gravure ink composition for adsorbing ammonia-based compounds, which is used for an ammonia-based compound adsorption printed matter having a substrate and an ammonia-based compound adsorption layer having a thickness of 0.1 to 5 μm on at least one side of the substrate, The gravure ink composition for adsorbing ammonia-based compounds contains an acidic group-containing thermoplastic resin (A) and a solvent (B). fruit, The acidic group-containing thermoplastic resin (A) the resin is at least one of an acrylic resin obtained by copolymerizing at least one of a (meth)acrylic acid ester having a hydrocarbon chain, a (meth)acrylic acid ester having a hydroxyl group, a (meth)acrylic acid ester having an amino group, a (meth)acrylic acid ester having a sulfonic group, a (meth)acrylic acid ester having a phosphoric acid group, and a (meth)acrylic acid ester having a carboxyl group with at least one of (meth)acrylic acid, a (meth)acrylic acid ester having a carboxyl group, a (meth)acrylic acid ester having a sulfonic acid group, and a (meth)acrylic acid ester having a phosphoric acid group; a styrene-unsaturated carboxylic acid copolymer; a rosin-based resin; an acid-modified chloride-vinyl acetate copolymer; and a methacrylic acid homopolymer; The solvent (B) at least one of aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, ester solvents, ketone solvents, glycol ether solvents, and esterified products thereof; The substrate is At least one of paper, PET film, polyethylene film, polypropylene film, polyamide film, coating film, transparent vapor-deposited polyester film or transparent vapor-deposited polyamide film, and co-extruded film A gravure ink composition for adsorbing ammonia-based compounds, (2) A gravure ink composition for adsorbing ammonia-based compounds, which is used for an ammonia-based compound adsorption printed matter having a substrate and an ammonia-based compound adsorption layer having a thickness of 0.1 to 5 μm on at least one side of the substrate, The gravure ink composition for adsorbing ammonia-based compounds contains, when the total weight of the gravure ink composition for adsorbing ammonia-based compounds is 100% by weight, an acidic group-containing thermoplastic resin (A) in an amount of 1 to 99% by weight, calculated as a solid content, and a solvent (B) in an amount of 1 to 99% by weight, The acidic group-containing thermoplastic resin (A) the resin is at least one of an acrylic resin obtained by copolymerizing at least one of a (meth)acrylic acid ester having a hydrocarbon chain, a (meth)acrylic acid ester having a hydroxyl group, a (meth)acrylic acid ester having an amino group, a (meth)acrylic acid ester having a sulfonic group, a (meth)acrylic acid ester having a phosphoric acid group, and a (meth)acrylic acid ester having a carboxyl group with at least one of (meth)acrylic acid, a (meth)acrylic acid ester having a carboxyl group, a (meth)acrylic acid ester having a sulfonic acid group, and a (meth)acrylic acid ester having a phosphoric acid group; a styrene-unsaturated carboxylic acid copolymer; a rosin-based resin; an acid-modified chloride-vinyl acetate copolymer; and a methacrylic acid homopolymer; The solvent (B) at least one of aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, ester solvents, ketone solvents, glycol ether solvents, and esterified products thereof; The substrate is At least one of paper, PET film, polyethylene film, polypropylene film, polyamide film, coating film, transparent vapor-deposited polyester film or transparent vapor-deposited polyamide film, and co-extruded film A gravure ink composition for adsorbing ammonia-based compounds, [Means for solving the problem]

[0008] The present inventors have found that the above problems can be solved by a gravure ink composition for adsorbing ammonia-based compounds, which contains an acidic group-containing thermoplastic resin and a solvent, and have thus completed the present invention.

[0009] That is, the present invention is (1) A gravure ink composition for adsorbing ammonia-based compounds, which is used for an ammonia-based compound adsorption printed matter having a substrate and an ammonia-based compound adsorption layer having a thickness of 0.1 to 5 μm on at least one side of the substrate, The gravure ink composition for adsorbing ammonia-based compounds comprises an acidic group-containing thermoplastic resin (A) and a solvent (B); (2) The gravure ink composition for adsorbing ammonia-based compounds according to (1), wherein the acidic group-containing thermoplastic resin (A) is at least one of a copolymer having an A block having a structural unit derived from a (meth)acrylic vinyl monomer represented by the following general formula (1) and a B block having a structural unit represented by the following general formula (2), a carboxyl group-containing urethane resin, a rosin-based resin, an acid-modified chloride-vinyl acetate copolymer, and an acid-modified polyester resin;

[0012] (3) The gravure ink composition for adsorbing ammonia-based compounds according to (1) or (2) forms an ammonia-based compound adsorption layer on at least one surface of a substrate, the ink layer having a thickness of 0.1 to 5 μm. death, The substrate is At least one of paper, PET film, polyethylene film, polypropylene film, polyamide film, coating film, transparent vapor-deposited polyester film or transparent vapor-deposited polyamide film, and co-extruded film A printed matter adsorbing an ammonia-based compound, (4) The gravure ink composition for adsorbing ammonia-based compounds according to (1) or (2) forms an ammonia-based compound adsorption layer on at least one surface of a substrate, the ink layer having a thickness of 0.1 to 5 μm, and a laminate layer or a pressure-sensitive adhesive layer is laminated on the ammonia-based compound adsorption layer or on the substrate on the opposite side of the ammonia-based compound adsorption layer. the law of nature, The substrate is At least one of paper, PET film, polyethylene film, polypropylene film, polyamide film, coating film, transparent vapor-deposited polyester film or transparent vapor-deposited polyamide film, and co-extruded film A laminate characterized by: (5) The laminate according to (4), wherein the laminate layer is a sealant layer or a sealing layer. (6) The laminate according to (4) or (5), wherein the laminate layer is at least one laminate layer selected from the group consisting of dry laminate, non-solvent laminate, thermal laminate, extrusion laminate, coextrusion laminate, and PE sandwich laminate. (7) preparing a substrate; a gravure printing step of printing the gravure ink composition for adsorbing ammonia-based compounds according to claim 1 or 2 on at least one of the substrates to form an adsorption layer for ammonia-based compounds with a thickness of 0.1 to 5 μm. fruit, The substrate is At least one of paper, PET film, polyethylene film, polypropylene film, polyamide film, coating film, transparent vapor-deposited polyester film or transparent vapor-deposited polyamide film, and co-extruded film A method for producing an ammonia-based compound adsorbent printed material, (8) preparing a substrate; a gravure printing step of forming an ammonia compound adsorption layer by printing the gravure ink composition for adsorbing ammonia compounds according to claim 1 or 2 on at least one of the substrates in a film thickness of 0.1 to 5 μm; a laminating step or a coating step of forming a laminate layer or a pressure-sensitive adhesive layer on the ammonia-based compound adsorption layer or on the substrate on the opposite side of the ammonia-based compound adsorption layer; Including fruit, The substrate is At least one of paper, PET film, polyethylene film, polypropylene film, polyamide film, coating film, transparent vapor-deposited polyester film or transparent vapor-deposited polyamide film, and co-extruded film A method for producing a laminate, (9) The method for producing a laminate according to (8), wherein the laminating step is a laminating step for forming a sealant layer, or the coating step is a coating step for forming a sealing layer or a pressure-sensitive adhesive layer. (10) The method for producing a laminate according to (8) or (9), wherein the lamination step is a lamination step for forming at least one laminate layer among a dry lamination step, a non-solvent lamination step, a thermal lamination step, an extrusion lamination step, a co-extrusion lamination step, and a PE sandwich lamination step. (11) A packaging bag essentially comprising a substrate, an ammonia-based compound adsorption layer laminated to a thickness of 0.1 to 5 μm, and a sealant layer or a sealing layer, wherein the ammonia-based compound adsorption layer is formed from the gravure ink composition for adsorbing ammonia-based compounds according to (1) or (2). R, The substrate is At least one of paper, PET film, polyethylene film, polypropylene film, polyamide film, coating film, transparent vapor-deposited polyester film or transparent vapor-deposited polyamide film, and co-extruded film A packaging bag characterized by: (12) A packaging container essentially comprising a substrate, an ammonia-based compound adsorption layer laminated to a thickness of 0.1 to 5 μm, and an extrusion laminate layer, wherein the ammonia-based compound adsorption layer is formed from the gravure ink composition for adsorbing ammonia-based compounds according to (1) or (2). R, The substrate is At least one of paper, PET film, polyethylene film, polypropylene film, polyamide film, coating film, transparent vapor-deposited polyester film or transparent vapor-deposited polyamide film, and co-extruded film A packaging container characterized by: It is related to. [Effects of the Invention]

[0013] The present invention can provide an ammonia-based compound-absorbing gravure ink composition that can suppress unpleasant ammonia-based compound odors that occur in living environments, such as the fishy odor of meat products such as meat and seafood, the putrid odor that occurs when these products decay, the odor of food waste, the odor of excretion in toilets, cigarette smoke, and body odor, and can also produce printable printed matter using a simple printing process. DETAILED DESCRIPTION OF THE INVENTION

[0014] Hereinafter, an embodiment of the present invention will be described in detail. Note that this embodiment is merely one embodiment of the present invention, and the present invention is not limited to this embodiment, and various modifications and embodiments are possible without departing from the gist of the present invention.

[0015] In the following description, (meth)acrylic and (meth)acrylate mean acrylic and methacrylic, acrylate and methacrylate, respectively.

[0016] The gravure ink composition for adsorbing ammonia-based compounds of the present invention (hereinafter also simply referred to as "adsorption ink composition") is used for an ammonia-based compound adsorption printed matter having a substrate and an ammonia-based compound adsorption layer having a film thickness of 0.1 to 5 μm on at least one side of the substrate, and The gravure ink composition for adsorbing ammonia-based compounds preferably contains an acidic group-containing thermoplastic resin (A) and a solvent (B).

[0017] The gravure ink composition for adsorbing ammonia compounds of the present invention preferably contains an acidic group-containing thermoplastic resin (A), and the acidic group reacts with the ammonia compound to form a bond, thereby reducing odor and suppressing the ammonia odor.

[0018] The acidic group-containing thermoplastic resin (A) is more preferably at least one of a copolymer having an A block having a structural unit derived from a (meth)acrylic vinyl monomer represented by the following general formula (1) and a B block having a structural unit represented by the following general formula (2), a carboxyl group-containing urethane resin, a rosin resin, an acid-modified chloride-vinyl acetate copolymer, and an acid-modified polyester resin.

[0019] [ka]

[0020] In formula (1), R 1 ~R 4 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, COOM, R 9 R is either COOM, OH, or an aryl group, and may be the same or different. 9 is an alkylene group having 0 to 5 carbon atoms, and the alkylene group having 0 to 5 carbon atoms is R 9 The carbon atoms at both ends of the group are directly bonded. M may be a hydrogen atom, an alkali metal, an alkyl group having 1 to 6 carbon atoms, or an alkanol group having 1 to 6 carbon atoms. m represents the number of moles of the respective structural units, and is an integer of 0 to 20.

[0021] As the (meth)acrylic vinyl monomer, (meth)acrylic acid and / or (meth)acrylic acid esters can be used. Examples of the (meth)acrylic acid esters include (meth)acrylic acid esters having a hydrocarbon chain, (meth)acrylic acid esters having a hydroxyl group, (meth)acrylic acid esters having an amino group, (meth)acrylic acid esters having an epoxy group, (meth)acrylic acid esters having a sulfone group (also referred to as a sulfo group or sulfonic acid group), (meth)acrylic acid esters having a phosphate group, and (meth)acrylic acid esters having a carboxyl group. Of these, (meth)acrylic acid, (meth)acrylic acid esters having a hydrocarbon chain, (meth)acrylic acid esters having a hydroxyl group, (meth)acrylic acid esters having an amino group, (meth)acrylic acid esters having a sulfone group, (meth)acrylic acid esters having a phosphate group, and (meth)acrylic acid esters having a carboxyl group are more preferred.

[0022] Examples of the (meth)acrylic acid ester having a hydrocarbon chain include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cumyl (meth)acrylate, cyclohexyl (meth)acrylate, myristyl (meth)acrylate, lauryl (meth)acrylate, palmityl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate, etc. Among these, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and n-butyl (meth)acrylate are more preferred.

[0023] Examples of the (meth)acrylic acid ester having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 12-hydroxylauryl (meth)acrylate, and ethyl-α-(hydroxymethyl) Monofunctional (meth)acrylic acid esters such as (meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolethane di(meth)acrylate, 2-hydroxy-3-(meth)acryloxypropyl (meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate acrylate, polyfunctional (meth)acrylic acid esters such as tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, fatty acid ester-based (meth)acrylic acid esters such as (meth)acrylic acid glycidyl laurate, cyclic (meth)acrylic acid esters such as cyclohexanedimethanol mono(meth)acrylate, cyclohexanediethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and 2-a(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, aliphatic (meth)acrylic acid esters such as (meth)acrylic acid esters having hydroxyl groups at the molecular terminals by ring-opening addition of ε-caprolactone to the above-mentioned (meth)acrylic acid esters having hydroxyl groups, and alkylene oxide-added (meth)acrylic acid esters obtained by repeatedly adding alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide to the above-mentioned (meth)acrylic acid esters having hydroxyl groups. Of these, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, and the like are more preferred.

[0024] Examples of the (meth)acrylic acid ester having an amino group include dimethylaminomethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminomethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, diethylaminopropyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, dipropylaminomethyl (meth)acrylate, dipropylaminoethyl (meth)acrylate, dipropylaminopropyl (meth)acrylate, diisopropylaminoethyl (meth)acrylate, dibutylaminoethyl (meth)acrylate, and diisobutylaminoethyl (meth). ) acrylate, di-t-butylaminoethyl (meth)acrylate, methylethylaminoethyl (meth)acrylate, methylpropylaminopropyl (meth)acrylate, 1-(t-butylamino)ethyl (meth)acrylate, 1-(t-butylamino)propyl (meth)acrylate, 2-(t-butylamino)ethyl (meth)acrylate, and the like, and among these, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminomethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and methylethylaminoethyl (meth)acrylate are more preferred.

[0025] Examples of the (meth)acrylic acid ester having a sulfonic acid group include (meth)acrylic sulfonic acid, 2-(sulfoxy)ethyl methacrylic acid, 3-sulfopropyl acrylic acid, and 3-sulfopropyl methacrylic acid.

[0026] Examples of the (meth)acrylic acid ester having a phosphate group include compounds represented by the following general formulas (3) to (5). CH2=CRCOO(R 10 O) n P=O(OR 11 )2(3) In the formula, R represents a hydrogen atom or a methyl group. 10 represents an alkylene group having 1 to 4 carbon atoms, R 11represents an alkylene group having 1 to 8 carbon atoms, and n represents an integer of 1 to 8. [CH2=CRCOO(R 10 O) n ] m P=O(OR 12 ) 3-m (4) In the formula, R, R 10 is the same as Equation 3, R 12 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; n represents an integer of 1 or 2; and m represents an integer of 2 or 3. CH2=CRCOO(R 10 O) n P=O(O-Ph) m (OH) 2-m (5) In the formula, R, R 10 As in formula 3, Ph represents a benzene ring, n represents an integer of 1 or 2, and m represents an integer of 0 to 2.

[0027] Examples of the (meth)acrylic acid ester having a carboxyl group include, in addition to the (meth)acrylic acid, monohydroxyethyl phthalate acrylate, p-carboxybenzyl acrylate, ethylene oxide-modified (number of moles added: 2 to 18) acrylate phthalate, monohydroxypropyl phthalate, monohydroxyethyl succinate acrylate, β-carboxyethyl acrylate, and 2-(4-benzoyl-3-hydroxyphenoxy)ethyl acrylate.

[0028] The structural units derived from the (meth)acrylic vinyl monomer in the A block may be of one type or two or more types.

[0029] When the A block contains two or more types of structural units, the various structural units contained in the A block may be contained in the A block in any polymerization form such as random copolymerization or block copolymerization, and from the viewpoint of uniformity, they are preferably contained in the A block in the form of random copolymerization. For example, the A block may be formed from a copolymer of structural units consisting of the a1 block and structural units consisting of the a2 block.

[0030] [ka]

[0031] In formula (2), R 5 ~R 7 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, COOM, R 9 R is either COOM, OH, or an aryl group, and may be the same or different. 8 , R 9 is an alkylene group having 0 to 5 carbon atoms, and the alkylene group having 0 to 5 carbon atoms is R 8 , R 9 The carbon atoms at both ends of the formula (1) are directly bonded. M may be a hydrogen atom, an alkali metal, an alkyl group having 1 to 6 carbon atoms, or an alkanol group having 1 to 6 carbon atoms. X is an acidic group. n represents the number of moles of each structural unit, and n is an integer of 1 to 50. When m in the formula (1) is 0, the resulting polymer is a homopolymer composed of structural units whose number of moles is represented by n.

[0032] In the general formula (2), the acidic group represented by X is -COOM (carboxyl group), -SO3M (sulfo group), -OP=O(OH)2 (phosphate group), -P=O(OH)2 (phosphonate group), -P=O(OH)R 13 (phosphinic acid group). 13 is any one of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, OH, and an aryl group. M may be any one of a hydrogen atom, an alkali metal, an alkyl group having 1 to 6 carbon atoms, and an alkanol group having 1 to 6 carbon atoms.

[0033] Examples of compounds that form the structural unit represented by general formula (2) include (meth)acrylic acid esters having a carboxy group, such as monomers obtained by reacting hydroxyalkyl (meth)acrylate with acid anhydrides such as maleic anhydride, succinic anhydride, and phthalic anhydride; (meth)acrylic acid esters having a sulfonic acid group, such as ethyl (meth)acrylate sulfonate; and (meth)acrylic acid esters having a phosphate group, such as 2-(phosphonooxy)ethyl (meth)acrylate and the compounds represented by formulas (3) to (5). Of these, (meth)acrylic acid, (meth)acrylic acid esters having a carboxy group, and (meth)acrylic acid esters having a phosphate group are preferred, with (meth)acrylic acid being more preferred. These may be of one type or two or more types.

[0034] The copolymer having an A block having a structural unit derived from a (meth)acrylic vinyl monomer represented by the general formula (1) and a B block having a structural unit represented by the general formula (2) may be a block copolymer or a random copolymer. The two terminals are not particularly limited and may be the same or different, such as a hydrogen atom, OH, an alkyl group having 1 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, or SO3M. M may be a hydrogen atom, an alkali metal, an alkyl group having 1 to 6 carbon atoms, or an alkanol group having 1 to 6 carbon atoms.

[0035] Examples of the copolymer having an A block having a structural unit derived from a (meth)acrylic vinyl monomer represented by the general formula (1) and a B block having a structural unit represented by the general formula (2) include an acrylic resin, an acrylic acid-unsaturated carboxylic acid copolymer, an olefin-unsaturated carboxylic acid copolymer, a styrene-unsaturated carboxylic acid copolymer, a (meth)acrylic acid homopolymer, and an itaconic acid homopolymer.

[0036] The weight-average molecular weight of the acrylic resin is preferably 20,000 to 200,000, and more preferably 30,000 to 110,000. An acrylic resin with a weight-average molecular weight of less than 20,000 is undesirable because poor adhesion is likely to occur due to insufficient cohesion, while a weight-average molecular weight of more than 200,000 results in high resin viscosity. The weight-average molecular weight can be evaluated as a polystyrene-equivalent molecular weight using gel permeation chromatography (GPC).

[0037] The acrylic acid-unsaturated carboxylic acid copolymer is obtained by copolymerizing (meth)acrylic acid and an unsaturated carboxylic acid, and the unsaturated carboxylic acid is preferably an unsaturated carboxylic acid other than (meth)acrylic acid, such as maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, sorbic acid, mesaconic acid, and angelic acid. Examples of derivatives thereof include acid hydrates, esters, amides, imides, and metal salts, such as maleic anhydride, itaconic anhydride, citraconic anhydride, maleic acid monoethyl ester, acrylamide, maleic acid monoamide, maleimide, N-butylmaleimide, sodium acrylate, and sodium methacrylate. Of these, maleic anhydride is preferred. These may be of one type or two or more types. As the acrylic acid-unsaturated carboxylic acid copolymer, an acrylic acid-maleic acid copolymer is more preferred.

[0038] The olefin-unsaturated carboxylic acid copolymer is obtained by copolymerizing an olefin with an unsaturated carboxylic acid. The olefin is preferably one or more monomers selected from ethylene and α-olefins having 3 to 28 carbon atoms, such as propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, and 1-icosene. Of these, a propylene homopolymer, a copolymer of propylene and an α-olefin, an ethylene homopolymer, and a copolymer of ethylene and an α-olefin are preferred, and propylene and 1-butene are more preferred. These may be of one type or two or more types.

[0039] The unsaturated carboxylic acid is preferably one of those mentioned above, and among them, maleic anhydride and (meth)acrylic acid are more preferred. These may be of one type or two or more types. Examples of the olefin-unsaturated carboxylic acid copolymer include maleic anhydride-modified polypropylene, ethylene-(meth)acrylic acid copolymer, ethylene-acrylic acid ester-maleic anhydride terpolymer, and ethylene-methacrylic acid ester-maleic anhydride terpolymer, with maleic anhydride-modified polypropylene and ethylene-(meth)acrylic acid copolymer being more preferred.

[0040] The styrene-unsaturated carboxylic acid copolymer is obtained by copolymerizing styrene with an unsaturated carboxylic acid, and the unsaturated carboxylic acid is preferably (meth)acrylic acid or one of the above, and particularly preferably (meth)acrylic acid or maleic anhydride. These may be of one type or two or more types. As the styrene-unsaturated carboxylic acid copolymer, a styrene-acrylic copolymer and a styrene-maleic acid copolymer are more preferred.

[0041] The (meth)acrylic acid homopolymer and the itaconic acid homopolymer are copolymers having an A block having a structural unit derived from the (meth)acrylic vinyl monomer represented by the general formula (1) and a B block having a structural unit represented by the general formula (2), in which m is 0, and R 5 , R 6 is a hydrogen atom, R 7 COOM, or R 9 COOH or R 8 , R 9 is an alkylene group having 0 to 5 carbon atoms, and the alkylene group having 0 to 5 carbon atoms is R 8 , R 9 The carbon atoms at both ends of the group are directly bonded. M is a hydrogen atom or a methyl group, and it is a polymer made of a simple compound. n is an integer of 1 to 50. Among these, methacrylic acid homopolymer is more preferred.

[0042] The carboxyl group-containing urethane resin is preferably a polymer obtained by reacting a polyurethane resin as a main component with at least a polyol, a hydroxy acid, a diisocyanate compound, and a chain extender, or may be an unsaturated carboxylic acid-modified polyurethane resin obtained by adding an unsaturated carboxylic acid to a polymer obtained by reacting at least a polyol, a diisocyanate compound, and a chain extender.

[0043] The polyol is preferably a polyester polyol, more preferably a polyester containing a diol and a dicarboxylic acid. The number average molecular weight of the polyester polyol is preferably 1000 to 6000. The number average molecular weight can be evaluated as a polystyrene-equivalent molecular weight using gel permeation chromatography (GPC).

[0044] Examples of diols constituting the polyester polyol include ethylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, triethylene glycol, 2-methyl-1,3-butylene glycol, 1-methyl-1,3-butylene glycol, 2-methyl-1,3-butylene glycol, 1-methyl-1,4-pentylene glycol, 2-methyl-1,4-pentylene glycol, 2,4-diethyl-1,5-pentanediol, tripropylene glycol, 1,2-propylene glycol, 1,3-butanediol, Examples of suitable alkylene oxides include 1-methyl-1,5-pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, alkylene oxide adducts of bisphenol A such as ethylene oxide, propylene oxide, and ethylene propylene oxide, neopentyl glycol, and butylethylpropanediol. Of these, 3-methyl-1,5-pentanediol and neopentyl glycol are more preferred. These may be of one type or two or more types.

[0045] The polyester polyol may further contain a multifunctional polyol, such as glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, sorbitol, and pentaerythritol.

[0046] Examples of dicarboxylic acids constituting polyester polyols include adipic acid, succinic acid, sebacic acid, azelaic acid, fumaric acid, maleic acid, terephthalic acid, isophthalic acid, etc. Among these, adipic acid and sebacic acid are more preferred. These may be of one type or two or more types.

[0047] The polyester polyol can be obtained by the same method as that for producing a normal polyester, that is, by dehydration condensation of a diol and a dicarboxylic acid or an acid anhydride.

[0048] The carboxyl group-containing urethane resin of the present invention can be obtained by reacting the polyester polyol with a hydroxy acid and other monomers. Examples of hydroxy acids include dimethylolalkanoic acids such as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolvaleric acid, and 2,2-dimethylolbutyric acid, and among these, 2,2-dimethylolpropionic acid and 2,2-dimethylolbutyric acid are more preferred. These may be of one type or two or more types.

[0049] The unsaturated carboxylic acid-modified polyurethane resin can be obtained by various known methods. Preferred unsaturated carboxylic acids include maleic acid, maleic anhydride, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid, and methacrylic acid. Of these, maleic acid-modified polyurethane resins are more preferred. These may be of one type or two or more types.

[0050] The diisocyanate compound is preferably an aromatic, aliphatic or alicyclic diisocyanate compound, and examples thereof include 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, Examples of the isocyanate include cyclohexane-1,4-diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, methylcyclohexane diisocyanate, m-tetramethylxylylene diisocyanate, and dimer diisocyanate in which the carboxyl group of a dimer acid is converted to an isocyanate group, and among these, isophorone diisocyanate is more preferred. These may be of one type or two or more types.

[0051] The chain extender is preferably a polyamine or glycol, and examples thereof include ethylenediamine, propylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, dicyclohexylmethane-4,4'-diamine, and dimer diamine. Other examples include diamines having a hydroxyl group in the molecule, such as 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, and di-2-hydroxypropylethylenediamine; the glycols exemplified above as polyols constituting polyester polyols, and other glycols; and diols having a tertiary amine structure, such as methyldiethanolamine, methyldiisopropanolamine, phenyldiisopropanolamine, 4-methylphenyldiisopropanolamine, and 4-methylphenyldiethanolamine. Among these, isophoronediamine and dibutylamine are more preferred. These may be of one type or two or more types.

[0052] Furthermore, when synthesizing the polyurethane resin, a chain terminator can be used as needed. Examples of the chain terminator include monoalcohols and monoamines. Examples of monoalcohols include methanol, propanol, butanol, and 2-ethylhexanol. Examples of monoamines include mono- or di-alkylamines having 2 to 8 carbon atoms (butylamine, dibutylamine, etc.) and mono- or di-alkanolamines having 2 to 6 carbon atoms (monoethanolamine, diethanolamine, propanolamine, etc.).

[0053] Polyurethane resins can be synthesized by reacting a material mixture containing a polyol, a hydroxy acid, and a diisocyanate compound to produce a urethane prepolymer having a urethane bond and an isocyanate group at its terminal, and then reacting the urethane prepolymer with a chain extender to produce a polyurethane urea resin. The contents of the polyol, diisocyanate compound, and chain extender can be adjusted as desired, and the synthesis conditions can be set appropriately according to conventional methods for synthesizing polyurethane resins.

[0054] Examples of the rosin-based resin include rosin and rosin derivatives. Rosin can be obtained by polymerizing natural rosin such as gum rosin, tall oil rosin, or wood rosin in an organic solvent such as toluene or xylene in the presence of a non-halogen catalyst such as a mineral acid such as sulfuric acid, an organic acid such as formic acid, or a sulfonic acid catalyst such as paratoluenesulfonic acid or methylsulfonic acid, and then removing the catalyst, solvent, and, in some cases, unreacted rosin by means of distillation or the like. Although the polymerization method is not particularly limited, it is preferably a method using a polymer catalyst having an acidic functional group such as a sulfonic acid group. The non-halogen catalyst used is preferably a sulfonic acid catalyst, more preferably paratoluenesulfonic acid or methylsulfonic acid.

[0055] The rosin derivative may be any of various modified polymerized rosins, such as stabilized polymerized rosins obtained by disproportionating or hydrogenating polymerized rosins, or unsaturated acid-modified polymerized rosins obtained by adding unsaturated carboxylic acids to polymerized rosins. These derivatives can be obtained by various known methods. Preferred unsaturated carboxylic acids include maleic acid, maleic anhydride, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid, and methacrylic acid. Among these, polymerized rosin and maleic acid-modified rosin resin are more preferred. These may be of one type or two or more types.

[0056] The number average molecular weight of the rosin resin is preferably 500 to 7,000, and more preferably 800 to 5,000.

[0057] The acid-modified vinyl chloride copolymer is obtained by copolymerizing vinyl chloride monomer, vinyl acetate monomer, and a monomer having an unsaturated carbon-carbon double bond in one molecule and an acidic functional group, and can be produced by a conventionally known polymerization method without any particular limitation, and can be any of solution polymerization, emulsion polymerization, and suspension polymerization. Examples of the acidic functional group include a carboxyl group, a sulfonic acid group, a mercapto group, a lactone group, a phenol group, and a quinone group, with a carboxyl group being more preferred.

[0058] Examples of monomers having a carboxyl group include monocarboxylic acids such as (meth)acrylic acid, acetic acid, propionic acid, butyric acid, valeric acid, isovaleric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, and salicylic acid. Examples of dicarboxylic acids include malic acid, itaconic acid, maleic acid (anhydride), phthalic acid, oxalic acid, glutaric acid, malonic acid, terephthalic acid, fumaric acid, isophthalic acid, adipic acid, sebacic acid, and succinic acid. Of these, maleic acid (anhydride) is more preferred. Among these, maleic acid-modified vinyl chloride-acetate copolymer is more preferred. These may be of one type or two or more types.

[0059] The acid-modified polyester resin is preferably an ester compound of a carboxylic acid and an alcohol having 2 to 12 carbon atoms, and an intramolecular acid anhydride of an unsaturated carboxylic acid is added to the hydroxyl group terminal of the carboxylic acid-modified polyester, thereby further adding a carboxyl group to the terminal of the carboxylic acid-modified polyester, thereby obtaining an unsaturated carboxylic acid-modified polyester resin.

[0060] Examples of alcohols having 2 to 12 carbon atoms include ethanol, propan-1-ol, butan-1-ol, pentan-1-ol, hexane-1-ol, heptan-1-ol, octan-1-ol, nonan-1-ol, decan-1-ol, undecane-1-ol, and dodecane-1-ol, and may also be polyhydric alcohols having two or more hydroxyl groups. Examples include alkylene glycols such as dipropylene glycol, ethylene glycol, propylene glycol, pentanediol, and hexanediol, and polyalkylene glycols having 12 or less carbon atoms such as diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, tripropylene glycol, and polypropylene glycol.

[0061] Examples of carboxylic acids include valeric acid, isovaleric acid, caproic acid, 2-ethylbutanoic acid, heptanoic acid, 2-methylhexanoic acid, 3-methylhexanoic acid, 2-ethylpentanoic acid, 3-ethylpentanoic acid, isoheptanoic acid, caprylic acid, 2-ethylhexanoic acid, nonanoic acid, 3,5,5-trimethylhexanoic acid, neononanoic acid, capric acid, neodecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, and arachic acid. Examples of polycarboxylic acids include succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, fumaric acid, maleic acid, trimellitic acid, and pyromellitic acid.

[0062] Examples of unsaturated carboxylic acids include (meth)acrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid, with maleic acid being more preferred. Of these, maleic acid-modified polyester resins are more preferred. These may be of one type or two or more types.

[0063] The acid value of the acidic group-containing thermoplastic resin (A) of the present invention is preferably 1 mgKOH / g to 1000 mgKOH / g, more preferably 50 mgKOH / g to 800 mgKOH / g, and even more preferably 100 mgKOH / g to 500 mgKOH / g. An acid value of less than 1 mgKOH / g is undesirable because it reduces the resolubility of the ink and may cause clogging or fogging, while an acid value of more than 1000 mgKOH / g may result in a decrease in the water resistance of the ink and a decrease in adhesion to the substrate layer.The acid value is the number of milligrams of potassium hydroxide required to neutralize the acid groups contained in 1 g of resin, and is measured according to JIS K0070.

[0064] The weight average molecular weight of the acidic group-containing thermoplastic resin (A) of the present invention is preferably 3,000 to 200,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. The weight average molecular weight can be evaluated as a polystyrene-equivalent molecular weight using gel permeation chromatography (GPC).

[0065] In the adsorption ink composition of the present invention, the acidic group-containing thermoplastic resin (A) is preferably contained in an amount of 1 to 99% by weight, more preferably 5 to 80% by weight, and even more preferably 10 to 50% by weight, calculated as solids. If the content of the acidic group-containing thermoplastic resin (A) is less than 1% by weight, the adsorption ability of the adsorption ink composition for ammonia compounds will be poor, while if the content of the acidic group-containing thermoplastic resin (A) is more than 99% by weight, the adsorption ink composition will have poor blocking resistance and poor solubility, which may result in clouding or gelation.

[0066] The gravure ink composition for adsorbing ammonia-based compounds of the present invention may contain other thermoplastic resins (a1) in addition to the acidic group-containing thermoplastic resin (A). Preferred examples of the resin include shellacs, cellulose acetate, cellulose acetyl propionate, cellulose acetyl butyrate, chlorinated rubber, cyclized rubber, polyethylene resin, polypropylene resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride resin, polyester resin, polyvinylidene chloride resin, vinyl acetate resin, ketone resin, butyral resin, chlorinated ethylene vinyl acetate resin, ethylene vinyl acetate resin, polystyrene resin, polyacetal resin, polycarbonate resin, casein, alkyd resin, acrylonitrile resin, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polysulfone resin, polyether resin, polyether sulfone resin, polyether ketone resin, modified polyphenylene ether resin, polyphenylene sulfone resin, polyimide resin, polyamide-imide resin, amorphous polyarylate resin, polyether ether ketone resin, polyvinyl alcohol resin, ethylene-vinyl alcohol resin, polylactic acid, acrylic resin not containing a carboxyl group, urethane resin, and vinyl chloride-vinyl acetate copolymer resin. These resins may be of one type or of two or more types. Commercially available products that can be used include TPH medium, VESTA medium, LRC-NT medium, KCNT medium, PULPTECC medium, LAMITECC medium, LG-FK medium, SYNA-S medium, and LAMREK medium (all manufactured by Tokyo Ink Co., Ltd.).

[0067] The total thermoplastic resin content in the adsorption ink composition of the present invention, which is the sum of the acidic group-containing thermoplastic resin (A) and the other thermoplastic resin (a1), is preferably 1 to 99% by weight, more preferably 5 to 80% by weight, and even more preferably 10 to 50% by weight, calculated on a solids basis. If the total thermoplastic resin content is less than 1% by weight, the film-forming ability of the adsorption ink composition will be poor, and if the total thermoplastic resin content is more than 99% by weight, the fluidity of the adsorption ink composition will be poor, making it less suitable for production.

[0068] The gravure ink composition for adsorbing ammonia-based compounds of the present invention can use a solvent (B) that is usually used in gravure inks. Examples of the solvent (B) include aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane, alcohol solvents such as methanol, ethanol, isopropyl alcohol, normal propyl alcohol, 1-butanol, 2-butanol, isobutanol, and tert-butanol, ester solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, and tert-butyl acetate, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, and ethylene glycol monomethyl ether. Examples of suitable solvents include glycol ether solvents such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether, as well as esters thereof. The esters are primarily acetated, such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. Among these, from the standpoint of printability and versatility, toluene, ethyl acetate, n-propyl acetate, isopropyl alcohol, methanol, propylene glycol monomethyl ether, and methyl ethyl ketone are more preferred. These solvents can be used alone or in combination. The solvent content in the adsorption ink composition is preferably within the range of 1 to 99% by weight. If it is less than 1% by weight, the solid content will be high, resulting in poor fluidity and poor ink manufacturing suitability, while if it exceeds 99% by weight, the ink film thickness will become locally non-uniform, irregular shading (swimming phenomenon) will occur on the printed surface, and the viscosity will be low, which may make the pigment more likely to settle.

[0069] The adsorption ink composition may also contain coloring materials, inorganic fillers, organic fillers, antifoaming agents, leveling agents, antiblocking agents, waxes, pigment dispersants, antistatic agents, slip agents, plasticizers, tackifiers, etc. Any known and commonly used agents may be appropriately selected within the range that does not impair the properties of the adsorption ink composition.

[0070] The coloring material may contain a pigment or a dye, or a mixture thereof. Examples of pigments include inorganic pigments such as titanium dioxide, red iron oxide, barium sulfate, calcium carbonate, silica, zinc oxide, zinc sulfide, mica, talc, and pearl; organic pigments such as phthalocyanine-based, insoluble azo-based, condensed azo-based, dioxazine-based, anthraquinone-based, quinacridone-based, perylene-based, perinone-based, thioindigo-based, and carbon black; and various other fluorescent pigments, metal powder pigments, and extender pigments. These pigments may be used alone or in combination of two or more. Dyes that are soluble or dispersible in solvents are preferred, and may be used alone or in combination of two or more. Among these, pigments are preferred from the viewpoint of durability.

[0071] The substrate is preferably at least one selected from paper, plastic film or sheet, and laminates thereof. Examples include polyester films such as polyethylene terephthalate (PET), polyethylene naphthalate, and polybutylene terephthalate; polyolefin films such as polyethylene, polypropylene, and ethylene-vinyl acetate; polystyrene films; alcohol-based films such as ethylene-vinyl alcohol and polyvinyl alcohol; polyamide films or barrier polyamide films with an intermediate barrier layer; polycarbonate films; polyacrylonitrile films; polyimide films; cellophane; moisture-proof cellophane; transparent vapor-deposited polyester films or transparent vapor-deposited polyamide films formed by depositing a layer of alumina or silica on PET or polyamide films; various coating films coated with polyvinylidene chloride resin, polyvinyl alcohol resin, polyacrylic acid resin, and the like; co-extruded films of PET and nylon; polylactic acid films; polyvinyl chloride; or polyvinyl chloride resin sheets (foamed PVC sheets, foamed PVC boards, rigid PVC sheets, flexible PVC sheets) such as polymers of vinyl chloride, vinyl chloride-vinyl acetate copolymer, and ethylene-vinyl acetate copolymer. These may be stretched or unstretched, and one or more types may be laminated. An appropriate material can be selected taking into consideration factors such as mechanical strength and dimensional stability. Furthermore, to improve the adhesion of the anchor coat layer or laminate layer, the printing surface may be subjected to corona treatment, low-temperature plasma treatment, flame treatment, solvent treatment, coating treatment, or the like, or may be pre-treated. Among these, PET film, polyethylene film, polypropylene film, polyamide film, coating film, transparent vapor-deposited polyester film or transparent vapor-deposited polyamide film, coextruded film, and the like are preferred. The thickness of the substrate is not particularly limited as long as it does not impair printability or winding suitability. For films, a thickness of 5 to 300 μm is preferred, and a thickness of 6 to 250 μm is more preferred. For sheets, a thickness of 50 μm to 5 mm is preferred, and a thickness of 100 μm to 3 mm is more preferred.Furthermore, when the substrate is a film having heat sealing properties such as a polyethylene film, the substrate itself may function as a sealant layer.

[0072] The paper substrate preferably includes at least one selected from coated paper, uncoated paper, and paper substrates laminated with a plastic film or the like. The paper substrate may be laminated with a thermoplastic resin or the like by methods such as dry lamination, non-solvent lamination, or extrusion lamination, or by laminating with an adhesive, or may be a combination of these. Laminates with heat-sealing properties can also be used as the paper substrate. Methods for imparting heat-sealing properties include laminating a known sealant film, resin coating by extrusion lamination, coating with a heat-sealing agent or hot melt, or heat-sealing resin processing by coextrusion. A layer imparted with heat-sealing properties by these methods is also called a heat-sealing layer. The thickness of the paper substrate is not particularly limited as long as it does not interfere with printability or winding suitability, but is preferably 5 to 800 μm, more preferably 6 to 600 μm.

[0073] In the ammonia-compound-adsorbing printed matter of the present invention, the gravure ink composition for adsorbing ammonia-compounds preferably forms an ammonia-compound-adsorbing layer on at least one surface of a substrate by laminating an ink layer. The ink layer preferably has a thickness of 0.1 to 5 μm, more preferably 0.3 to 3 μm. If the ink layer is thinner than 0.1 μm, the adsorption ability decreases. If the ink layer is thicker than 5 μm, the blocking resistance decreases.

[0074] The ammonia-based compound-adsorption layer is preferably formed by laminating an ink layer on at least one surface of a substrate. The ammonia-based compound-adsorption layer is preferably formed by coating using a gravure printing method. In particular, it is more preferably formed by coating using a gravure printing method using a multicolor gravure printing machine. The ammonia-based compound-adsorption layer may be a single ink layer formed by laminating a gravure ink composition for adsorbing ammonia-based compounds, or may include the ink layer and another ink layer formed by laminating another gravure ink composition. Furthermore, since it is formed by coating using a gravure printing method, not only full solid printing but also partial printing and reverse printing are possible. Depending on the final laminate configuration, the position of the substrate for forming the ammonia-based compound-adsorption layer may change, and the order of forming the ink layer and other ink layers may also change. That is, for example, an ammonia-based compound adsorption layer may be formed in a structure such as substrate / ink layer / other ink layer, and then another substrate may be laminated thereon by dry lamination or the like (substrate / ink layer / other ink layer / DL / other substrate). Alternatively, an ammonia-based compound adsorption layer may be formed in a structure such as substrate / other ink layer / ink layer (or multiple layers such as ink layer / other ink layer), and then another substrate may be laminated thereon by dry lamination or the like (substrate / other ink layer / ink layer / (other ink layer, etc. / )DL / other substrate). Furthermore, by using a printing machine with a reversing mechanism, ammonia-based compound adsorption printed matter having a structure with various other ink layers can be obtained. For example, an ammonia-based compound adsorption layer may be formed in a structure such as substrate / ink layer / other ink layer, and then the structure may be reversed to form another ink layer, and then another substrate may be laminated thereon by dry lamination or the like (other substrate / DL / other ink layer / substrate / ink layer / other ink layer / DL / other substrate).

[0075] In addition to the ammonia-based compound adsorption layer, the ammonia-based compound adsorption printed matter of the present invention may have an intermediate layer laminated thereon to impart or enhance properties such as rigidity, stiffness, gas barrier properties, aroma retention, moisture resistance, pinhole resistance, dead hole resistance, light blocking properties, and straight cut properties. When an intermediate layer is provided, the ammonia-based compound adsorption layer does not necessarily have to be applied to the substrate, and the ammonia-based compound adsorption layer may be provided on the intermediate layer. However, it is preferable that the gas barrier layer for imparting gas barrier properties not be provided closer to the source of the adsorbed substance than the ammonia-based compound adsorption layer.

[0076] Examples of the intermediate layer include plastic films, sheets, and laminates thereof. Examples of plastic films include polyester films such as polyethylene terephthalate (PET), polyethylene naphthalate, and polybutylene terephthalate; polyolefin films such as polyethylene, polypropylene, and ethylene-vinyl acetate; polystyrene films; alcohol-based films such as ethylene-vinyl alcohol and polyvinyl alcohol; polyamide films or barrier polyamide films with an intermediate barrier layer; polycarbonate films; polyacrylonitrile films; polyimide films; cellophane; moisture-proof cellophane; transparent vapor-deposited polyester films or transparent vapor-deposited polyamide films formed by depositing a layer of alumina or silica on PET or polyamide films; various coating films coated with polyvinylidene chloride resin, polyvinyl alcohol resin, polyacrylic acid resin, and the like; co-extruded films of PET and nylon; and polylactic acid films. These may be stretched or unstretched, and may be laminated together or comprise one or more types. An appropriate film can be selected taking into consideration mechanical strength, dimensional stability, and the like. To improve adhesion, the bonding surfaces may be subjected to corona treatment, low-temperature plasma treatment, flame treatment, solvent treatment, coating treatment, etc., or may be pre-treated. Treatment on both sides is preferred. The thickness of the intermediate layer may be within a range that does not impair printability or windability, and is preferably 5 to 300 μm, more preferably 6 to 250 μm.

[0077] The laminate of the present invention preferably comprises an ammonia-based compound adsorption layer formed by laminating an ink layer of the gravure ink composition for adsorbing ammonia-based compounds on at least one surface of a substrate, and a laminate layer or adhesive layer laminated on the ammonia-based compound adsorption layer or on the substrate on the opposite side of the ammonia-based compound adsorption layer. The ink layer preferably has a thickness of 0.1 to 5 μm, more preferably 0.3 to 3 μm. The laminate layer is preferably formed by dry lamination, non-solvent lamination, or wet lamination, thermal lamination (thermal lamination), resin coating by extrusion lamination (extrusion lamination, co-extrusion lamination, PE sandwich lamination), or a film coated with a coating agent. An adhesive layer or a pressure-sensitive adhesive layer may be provided on the substrate on the opposite side of the ammonia-based compound adsorption layer. The laminate layer may be a sealant layer or a sealing layer. Examples of the sealant layer include a laminate having heat-sealing properties, a layer formed by laminating a known sealant film, or a layer formed by resin coating using an extrusion lamination method. Examples of the sealing layer include a layer formed by coating a heat-sealing agent or a hot-melt agent. Examples of the pressure-sensitive adhesive layer include a layer formed by coating an adhesive or a pressure-sensitive adhesive.

[0078] As for the sealant layer, the lamination method can be appropriately selected depending on the substrate, application, configuration, etc., as long as sufficient sealing strength can be ensured. For example, lamination of a known sealant film via an adhesive to the ammonia-based compound adsorption layer on the substrate (dry lamination, non-solvent lamination, wet lamination), thermal lamination (thermal lamination), resin coating by extrusion lamination (extrusion lamination, co-extrusion lamination, PE sandwich lamination), etc. can be preferably used. The laminate can be produced by one of these methods or a combination of these methods. The thickness of the sealant layer is not particularly limited, but is preferably 2 to 200 μm for a sealant film and 1 to 100 μm for a resin coating by extrusion lamination.

[0079] Examples of the sealant film include polyolefin films such as polyethylene, polypropylene, ethylene-vinyl acetate, and copolymers thereof, as well as co-extruded and colored films thereof, polystyrene films, polyacrylonitrile films, and ethylene-vinyl alcohol resin films. These films may be stretched or unstretched, and may be laminated with one or more types of films.

[0080] When adhesives are used in the dry lamination method, non-solvent lamination method, wet lamination method, extrusion lamination method, etc., commercially available adhesives may be used. Examples include two-component or one-component urethane resin adhesives, acrylic, epoxy, polyester, polyethyleneimine, polybutadiene, water-based urethane, isocyanate, organic titanium, and starch-based water-soluble adhesives, as well as aqueous adhesives such as vinyl acetate emulsions. The adhesive can be applied to form the sealant layer using known application methods, such as a roll coater, reverse roll coater, gravure coater, microgravure coater, knife coater, bar coater, wire bar coater, die coater, or dip coater. The thickness of the adhesive is not particularly limited, but is preferably in the range of approximately 0.001 to 10 μm, and particularly preferably in the range of 0.01 to 5 μm.

[0081] Resins that can be used for resin coating by the extrusion lamination method include thermoplastic resins such as polyethylene resins such as LDPE, LLDPE, and HDPE, polypropylene resin, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, acid-modified polyolefin resins obtained by modifying polyethylene or polypropylene with maleic acid, fumaric acid, or the like, polystyrene resin, and polybutylene terephthalate resin, and these resins may be used alone or in combination.

[0082] The method for forming the sealing layer is appropriately selected depending on the substrate, application, and configuration, as long as sufficient sealing strength is ensured. For example, heat-sealing agents or hot-melt coatings are preferably used. The laminate can be produced by one of these methods or a combination of these methods. The thickness of the sealing layer is not particularly limited, but is preferably 1 to 50 μm for hot-melt adhesive coatings and 0.01 to 30 μm for heat-sealing agent coatings.

[0083] Examples of resins for heat-sealing agents include thermoplastic resins such as vinylidene chloride, shellacs, rosins, rosin-modified maleic acid resins, rosin-modified phenolic resins, nitrocellulose, cellulose acetate, cellulose acetylpropionate, cellulose acetylbutyrate, chlorinated rubber, cyclized rubber, polyamide resins, vinyl chloride-vinyl acetate copolymers, polyester resins, ketone resins, butyral resins, chlorinated polypropylene resins, chlorinated polyethylene resins, chlorinated ethylene vinyl acetate resins, ethylene vinyl acetate resins, (meth)acrylic resins, urethane resins, ethylene-vinyl alcohol resins, styrene-maleic acid resins, casein, and alkyd resins, which may be used singly or in combination. Examples of resins that may be used include those dissolved in solvents or those dispersed in water, such as acrylic emulsions, urethane emulsions, ethylene-vinyl alcohol emulsions, polyethylene emulsions, polypropylene emulsions, and ethylene vinyl acetate emulsions.

[0084] The laminate layer is preferably at least one of dry lamination, non-solvent lamination, thermal lamination, extrusion lamination, co-extrusion lamination, and PE sandwich lamination. The laminate layer can be produced by at least one of dry lamination, non-solvent lamination, thermal lamination, and resin coating by extrusion lamination (extrusion lamination, co-extrusion lamination, and PE sandwich lamination).

[0085] Resins that can be used for resin coating by the extrusion lamination method include thermoplastic resins such as polyethylene resins such as LDPE, LLDPE, and HDPE, polypropylene resins (homopolypropylene, random polypropylene, etc.), ethylene-vinyl acetate copolymers, ionomer resins, ethylene-acrylic acid copolymers, ethylene-ethyl acrylate copolymers, ethylene-methyl acrylate copolymers, ethylene-methacrylic acid copolymers, ethylene-methyl methacrylate copolymers, ethylene-propylene copolymers, methylpentene polymers, acid-modified polyolefin resins obtained by modifying polyethylene or polypropylene with maleic acid, fumaric acid, etc., polystyrene resins (general-purpose polystyrene (GPPS), high impact polystyrene (HIPS), expanded polystyrene (PSP), heat-resistant PSP, etc.), and polybutylene terephthalate resins, and these resins may be used alone or in combination.

[0086] The ammonia-based compound adsorption printed matter of the present invention is preferably used for packaging, food preservation, retort pouches, microwave ovens, agriculture, civil engineering, fishing, automobile interior / exterior applications, marine applications, daily necessities, building interior / exterior applications, housing equipment applications, medical / medical equipment applications, pharmaceutical applications, home appliances, furniture applications, stationery / office supplies applications, sales promotion applications, commercial applications, electrical / electronic industry applications, and industrial material applications, etc. Among these, packaging, automobile interior / exterior applications, daily necessities applications, building interior / exterior applications, furniture applications, stationery / office supplies applications, and sales promotion applications are more preferred.

[0087] The method for producing an ammonia-based compound adsorption printed matter of the present invention preferably includes a step of preparing a substrate, and a gravure printing step of printing the gravure ink composition for adsorbing ammonia-based compounds on at least one side of the substrate to form an ammonia-based compound adsorption layer. The thickness of the ammonia-based compound adsorption layer is preferably 0.1 to 5 μm, more preferably 0.3 to 3 μm. If it is less than 0.1 μm, the adsorption ability of ammonia-based compounds decreases. If it is more than 5 μm, the blocking resistance decreases.

[0088] The method for producing the ammonia-based compound adsorption printed matter may be a method for producing an ammonia-based compound adsorption layer alone formed by printing the gravure ink composition for adsorbing ammonia-based compounds, or may include a gravure printing step for producing the ammonia-based compound adsorption layer and another printed layer formed by printing another gravure ink composition, and is more preferably produced by a gravure printing step using a multicolor gravure printing machine.Furthermore, a gravure printing machine having a reversing mechanism may be used.

[0089] In addition to the ammonia-based compound adsorption layer, the process may include a step of forming an intermediate layer to impart or enhance properties such as rigidity, stiffness, gas barrier properties, aroma retention, moisture resistance, pinhole resistance, dead hole resistance, light blocking properties, linear cutting properties, etc. However, it is preferable that the gas barrier layer for imparting gas barrier properties is formed so as not to be located closer to the source of the adsorbed substance than the ammonia-based compound adsorption layer.

[0090] The method for producing a laminate of the present invention preferably includes the steps of: preparing a substrate; a gravure printing step of printing the gravure ink composition for adsorbing ammonia-based compounds on at least one side of the substrate in a film thickness of 0.1 to 5 μm to form an ammonia-based compound adsorption layer; and a laminating or coating step of forming a laminate layer or a pressure-sensitive adhesive layer on the ammonia-based compound adsorption layer or on the substrate on the side opposite to the ammonia-based compound adsorption layer. The laminating step is preferably a laminating step of forming at least one laminate layer selected from the group consisting of a dry laminating step, a non-solvent laminating step, a thermal laminating step, an extrusion laminating step, a co-extrusion laminating step, and a PE sandwich laminating step. An adhesive layer or a pressure-sensitive adhesive layer may be provided on the substrate on the opposite side of the ammonia-based compound adsorption layer. The laminating step may be a laminating step for forming a sealant layer, or the coating step may be a coating step for forming a sealing layer, or the coating step may be a coating step for forming a pressure-sensitive adhesive layer.

[0091] The lamination step for forming the sealant layer may be, for example, a step of laminating a laminate provided with heat sealability or a known sealant film, or a step of resin coating by extrusion lamination, and the coating step for forming the seal layer may be a step of coating a heat sealant or a hot melt agent, etc. Furthermore, the coating step for forming the pressure-sensitive adhesive layer may be a step of coating an adhesive or a pressure-sensitive adhesive, etc.

[0092] The packaging bag of the present invention essentially comprises a substrate, an ammonia-based compound-adsorption layer laminated to a thickness of 0.1 to 5 μm, and a sealant layer or a sealing layer, and it is preferable that the ammonia-based compound-adsorption layer is formed from the gravure ink composition for adsorbing ammonia-based compounds.

[0093] The packaging bag may be of any known type, such as two-sided seal, three-sided seal, four-sided seal, pillow seal, standing pouch, envelope seal, gusset, or weld seal.

[0094] The packaging container of the present invention essentially comprises a substrate, an ammonia-based compound-adsorption layer laminated to a thickness of 0.1 to 5 μm, and an extrusion laminate layer, and it is preferred that the ammonia-based compound-adsorption layer is formed from the gravure ink composition for adsorbing ammonia-based compounds.

[0095] The packaging container may be any of the well-known forms used for packaging purposes, such as cups, trays, bottles, containers, boxes, cases, food boxes, covers, lids, caps, labels, and in-mold cups.

[0096] The gravure ink composition for adsorbing ammonia-based compounds of the present invention can be produced by a known method by uniformly dissolving or dispersing an acidic group-containing thermoplastic resin, other thermoplastic resins, colorants, various additives, and the like in a solvent. For dissolving or dispersing, various agitators or dispersers can be used, such as a dissolver, roll mill, ball mill, bead mill, sand mill, attritor, paint shaker, agitator, Henschel mixer, colloid mill, pearl mill, ultrasonic homogenizer, wet jet mill, kneader, or homomixer. These devices may be used alone or in combination. If the adsorption ink composition contains air bubbles or coarse particles, these can degrade printability and print quality, so it is preferable to remove them using a known filter or centrifuge.

[0097] The viscosity of the gravure ink composition for adsorbing ammonia-based compounds is not particularly limited as long as it does not interfere with printing. Considering the manufacturability and handling of the ink composition used in gravure printing, the viscosity is preferably 10 to 1,000 mPa·s at 25°C. If the viscosity is less than 10 mPa·s, the pigment tends to settle out due to its low viscosity. If the viscosity is greater than 1,000 mPa·s, the fluidity is poor, causing problems during ink production and making it difficult to fill into containers. In this case, the viscosity can be measured using a commercially available viscometer such as a Brookfield viscometer or a cone-and-plate viscometer.

[0098] The adsorption ink composition is preferably used in gravure printing, and can be applied as is, but can also be diluted with a diluting solvent in a Zahn Cup #3 (manufactured by Rigo Co., Ltd.) to adjust the viscosity to the desired level depending on the coating conditions and coating effect. In this case, the viscosity is preferably 10 to 40 seconds at 25°C. If the viscosity is less than 10 seconds, the ink tends to swim, and if it is more than 40 seconds, transferability during printing becomes poor.

[0099] The dilution solvent may be any solvent capable of adjusting the viscosity of the adsorption ink composition, and examples thereof include organic solvents, and commercially available solvents may also be used without particular limitation. Examples of commercially available solvents include TA52 solvent (alcohol-based solvent), PU533 solvent (toluene-containing solvent), PU515 solvent (non-toluene-based solvent), SL9155 solvent (non-toluene-based solvent), CN104 solvent (non-toluene-based solvent), AC372 solvent (non-toluene-based solvent), PP575 solvent (toluene-containing solvent), SL9164 solvent (non-ketone-based solvent), and SL9170 solvent (non-ketone-based solvent) (all manufactured by Tokyo Ink Co., Ltd.).

[0100] If necessary, a curing agent can be added to the adsorption ink composition during printing. Examples of such curing agents include aromatic diisocyanates such as tolylene diisocyanate and 4,4'-diphenylmethane diisocyanate, aliphatic diisocyanates such as hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 4,4'-dicyclohexyl diisocyanate, and pentane-1,5-diisocyanate (Stabio PDI), and polyisocyanate-based curing agents such as modified versions of these compounds, such as trimethylolpropane trimer, isocyanurate, biuret, and allophanate. These curing agents can be used alone or in combination. Commercially available products include 24A-100, 22A-75, TPA-100, TSA-100, TSS-100, TAE-100, TKA-100, P301-75E, E402-808, E405-70B, AE700-100, D101, D201, and A201H (manufactured by Asahi Kasei Corporation), Mytec Y260A (manufactured by Mitsubishi Chemical Corporation), Coronate HX, Coronate HL, and Coronate L (manufactured by Tosoh Corporation), Desmodur N75MPA / X (manufactured by Covestro Japan Co., Ltd.), and LG Hardener C (manufactured by Tokyo Ink Co., Ltd.). [Example]

[0101] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these. In the examples and comparative examples, "parts" means "parts by mass" and "%" means "% by weight."

[0102] [Preparation of acrylic resin containing acidic groups] (Production Example 1) An acrylic resin solution A (solid content 40%, weight average molecular weight 40,000, acid value 78.4) containing an acrylic resin synthesized by a conventional method from 10 parts of acrylic acid, 50 parts of methyl methacrylate, 20 parts of butyl methacrylate, and 20 parts of 2-hydroxyethyl methacrylate and a 6 / 4 mixed solvent of ethyl acetate and isopropyl alcohol was obtained.

[0103] (Production Example 2) An acrylic resin solution B (solid content 40%, weight average molecular weight 40,000, acid value 65.6) containing an acrylic resin synthesized by a conventional method from 10 parts of methacrylic acid, 50 parts of methyl methacrylate, 20 parts of butyl methacrylate, and 20 parts of 2-hydroxyethyl methacrylate and a 6 / 4 mixed solvent of ethyl acetate and isopropyl alcohol was obtained.

[0104] (Production Example 3) An acrylic resin solution C (solid content 40%, weight average molecular weight 40,000, acid value 27.8) containing an acrylic resin synthesized by a conventional method from 5 parts of 2-methacryloyloxyethyl acid phosphate, 45 parts of methyl methacrylate, 20 parts of butyl methacrylate, and 20 parts of 2-hydroxyethyl methacrylate, and a 6 / 4 mixed solvent of ethyl acetate and isopropyl alcohol was obtained.

[0105] (Production Example 4) Acrylic resin solution D (solid content 40%, weight average molecular weight 40,000, acid value 15.1) was obtained containing an acrylic resin synthesized by a conventional method from 5 parts of ethyl methacrylate sulfonate, 45 parts of methyl methacrylate, 20 parts of butyl methacrylate, and 20 parts of 2-hydroxyethyl methacrylate, and a 6 / 4 mixed solvent of ethyl acetate and isopropyl alcohol.

[0106] [Preparation of acrylic resin] (Production Example 5) An acrylic resin solution E (solid content 40%, weight average molecular weight 40,000, acid value 0.1) containing an acrylic resin synthesized by a conventional method from 50 parts of methyl methacrylate, 30 parts of butyl methacrylate, and 20 parts of 2-hydroxyethyl methacrylate and a mixed solvent of ethyl acetate and isopropyl alcohol (6 / 4) was obtained.

[0107] [Preparation of carboxyl group-containing polyurethane resin] (Production Example 6) A round-bottom flask equipped with a stirrer, thermometer, water separator, and nitrogen gas inlet tube was charged with 12.78 parts of 3-methylpentanediol adipate (number average molecular weight 2,000), 6.39 parts of propylene glycol (number average molecular weight 2,000), 0.95 parts of 2,2-dimethylol butyric acid, and 7.1 parts of isophorone diisocyanate. The mixture was reacted under a nitrogen stream at 105 ° C for 6 hours to produce a urethane prepolymer. 18.14 parts of ethyl acetate were added to obtain 45.36 parts of a homogeneous urethane prepolymer solution. Subsequently, 45.36 parts of the urethane prepolymer solution was added to a mixture of 2.75 parts of isophorone diamine, 0.04 parts of n-dibutylamine, 30.85 parts of ethyl acetate, and 21 parts of isopropyl alcohol, and the mixture was reacted at 60 ° C for 3 hours. This resulted in a carboxyl group-containing polyurethane resin solution PUU1 having a resin solid content of 30%, a viscosity of 990 mPa·s / 25° C., a weight average molecular weight of 50,000, and an acid value of 17.3.

[0108] [Preparation of polyurethane resin] (Production Example 7) A round-bottom flask equipped with a stirrer, thermometer, water separator, and nitrogen gas inlet tube was charged with 18.33 parts of 3-methylpentanediol adipate (number average molecular weight 2,000), 4.58 parts of propylene glycol (number average molecular weight 2,000), and 5.09 parts of isophorone diisocyanate. The mixture was reacted under a nitrogen stream at 105 ° C for 6 hours to produce a urethane prepolymer. 18.67 parts of ethyl acetate was added to obtain 46.67 parts of a urethane prepolymer homogeneous solution. 46.67 parts of the urethane prepolymer solution was then added to a mixture of 1.97 parts of isophorone diamine, 0.03 parts of n-dibutylamine, 30.33 parts of ethyl acetate, and 21 parts of isopropyl alcohol, and the mixture was reacted at 60 ° C for 3 hours. This resulted in a polyurethane resin solution PUU2 with a resin solid content of 30%, a viscosity of 990 mPa·s / 25°C, a weight average molecular weight of 50,000, and an acid value of 0.3.

[0109] [Preparation of gravure ink composition for adsorbing ammonia-based compounds] Example 1 50 parts of the acrylic resin solution A (solid content 40%, acid value 78.4) prepared in Production Example 1, 25 parts of n-propyl acetate, and 25 parts of isopropyl alcohol were charged and stirred for 30 minutes with a mixer to prepare a gravure ink composition G1 for adsorbing ammonia-based compounds (abbreviation: adsorption ink G1).

[0110] Example 2 50 parts of acrylic resin solution B (solid content 40%, acid value 65.6) prepared in Production Example 2, 25 parts of n-propyl acetate, and 25 parts of isopropyl alcohol were charged and stirred for 30 minutes with a mixer to prepare gravure ink composition G2 for adsorbing ammonia-based compounds (abbreviation: adsorption ink G2).

[0111] Example 3 50 parts of the acrylic resin solution C (solid content 40%, acid value 27.8) prepared in Production Example 3, 25 parts of n-propyl acetate, and 25 parts of isopropyl alcohol were charged and stirred for 30 minutes with a mixer to prepare a gravure ink composition G3 for adsorbing ammonia-based compounds (abbreviation: adsorption ink G3).

[0112] Example 4 50 parts of acrylic resin solution D (solid content 40%, acid value 15.1) prepared in Production Example 4, 25 parts of n-propyl acetate, and 25 parts of isopropyl alcohol were charged and stirred for 30 minutes with a mixer to prepare gravure ink composition G4 for adsorbing ammonia-based compounds (abbreviation: adsorption ink G4).

[0113] Example 5 20 parts of polymerized rosin (Aradigm R-140, acid value 140, manufactured by Arakawa Chemical Industries, Ltd.) and 80 parts of toluene were charged and stirred for 30 minutes with a stirrer to prepare gravure ink composition G5 for adsorbing ammonia-based compounds (abbreviation: adsorption ink G5).

[0114] Example 6 20 parts of rosin-modified maleic acid resin (Marquid No. 33, acid value 303, manufactured by Arakawa Chemical Industries, Ltd.) and 80 parts of toluene were charged and stirred for 30 minutes with a stirrer to prepare gravure ink composition G6 for adsorbing ammonia-based compounds (abbreviation: adsorption ink G6).

[0115] Example 7 20 parts of styrene-maleic acid copolymer (Alastar 700, acid value 180, manufactured by Arakawa Chemical Industries, Ltd.), 30 parts of isopropyl alcohol, and 50 parts of n-propyl acetate were charged and stirred for 30 minutes with a stirrer to prepare gravure ink composition G7 for adsorbing ammonia-based compounds (abbreviation: adsorption ink G7).

[0116] Example 8 15 parts of maleic acid-modified vinyl chloride copolymer (Solvine M5, acid value 5.9, manufactured by Nissin Chemical Industry Co., Ltd.) and 85 parts of methyl ethyl ketone were charged and stirred for 30 minutes with a stirrer to prepare gravure ink composition G8 for adsorbing ammonia-based compounds (abbreviation: adsorption ink G8).

[0117] Example 9 40 parts of the carboxyl group-containing polyurethane resin PUU1 (acid value 17.3) prepared in Production Example 6, 9 parts of isopropyl alcohol, 25 parts of ethyl acetate, 25 parts of n-propyl acetate, and 1 part of an antiblocking agent (hydrophobic finely powdered silica, Silophorbic 200, manufactured by Fuji Silysia Chemical Ltd.) were charged and stirred for 30 minutes using a stirrer to prepare a gravure ink composition G9 for adsorbing ammonia-based compounds (abbreviation: adsorption ink G9).

[0118] Example 10 50 parts of methacrylic acid homopolymer (solid content 40%, acid value 652), 25 parts of isopropyl alcohol, and 25 parts of ethyl acetate were charged and stirred for 30 minutes with a mixer to prepare gravure ink composition G10 for adsorbing ammonia-based compounds (abbreviation: adsorption ink G10).

[0119] (Comparative Example 1) 50 parts of the acrylic resin solution E (solid content 40%, acid value 0.1) prepared in Production Example 5, 25 parts of n-propyl acetate, and 25 parts of isopropyl alcohol were charged and stirred for 30 minutes with a mixer to prepare gravure ink composition H1 (abbreviation: ink H1).

[0120] (Comparative Example 2) 15 parts of vinyl alcohol-modified vinyl chloride-vinyl acetate copolymer (Solvine AL, acid value -, manufactured by Nissin Chemical Industry Co., Ltd.) and 85 parts of methyl ethyl ketone were charged and stirred with a stirrer for 30 minutes to prepare gravure ink composition H2 (abbreviation: ink H2).

[0121] (Comparative Example 3) 40 parts of the polyurethane resin solution PUU2 (acid value 0.3) prepared in Production Example 7, 9 parts of isopropyl alcohol, 25 parts of ethyl acetate, 25 parts of n-propyl acetate, and 1 part of an anti-blocking agent (hydrophobic finely powdered silica, Silohorbic 200, manufactured by Fuji Silysia Chemical Ltd.) were charged and stirred for 30 minutes using a stirrer to prepare gravure ink composition H3 (abbreviation: ink H3).

[0122] [Table 1]

[0123] [Table 2]

[0124] [Production of ammonia-based compound adsorption print] (Examples 11 to 14, and 23 to 30) Using a solid plate on a gravure proofing machine GRAVO-PROOF (product number: CM-W, manufactured by Nissho Gravure Co., Ltd.), the adsorption ink G1 from Example 1 was diluted with a dilution solvent (40 parts MEK, 40 parts propyl acetate, 20 parts isopropyl alcohol) to a viscosity of 17 seconds using a Zahn cup No. 3.The ink was then printed at a film thickness of 1.1 μm on an 18 μm thick unstretched polystyrene film, Styrophane SPH (abbreviated as CPS, manufactured by Oishi Sangyo Co., Ltd.), to obtain adsorption print PR1. Similarly, adsorption prints PR2 to PR4 and PR12 to PR19 were obtained by changing the adsorption ink and film thickness as shown in Table 3.

[0125] (Examples 15-16 and 31-34) Furthermore, the base material is 50 g / m 2 Instead of using the gravure paper, one-sided gloss bleached kraft paper (abbreviation: paper, manufactured by Oji Materia Co., Ltd.), the absorbent ink G5 was printed at a film thickness of 1.0 μm to obtain absorbent print PR5. Similarly, as shown in Tables 3 and 4, the absorbent ink and film thickness were changed to obtain absorbent prints PR6 and PR20 to PR23, respectively.

[0126] (Examples 17 to 21 and 35 to 42) Furthermore, the substrate was changed to a 12 μm thick vapor-deposited polyethylene terephthalate film, Barrierox 1011HGCR (abbreviation: vapor-deposited PET, manufactured by Toray Advanced Film Co., Ltd.), and adsorption ink G7 was printed at a film thickness of 1.0 μm to obtain adsorption print PR7. Similarly, as shown in Tables 3 and 4, the adsorption ink and film thickness were changed to obtain adsorption prints PR8 to PR10 and PR24 to PR31, respectively.

[0127] (Examples 22 and 43-44) Furthermore, the substrate was changed to a 20 μm-thick stretched polypropylene film, Pylen P-2161 (abbreviation: OPP, manufactured by Toyobo Co., Ltd.), and adsorption ink G9 was printed at a film thickness of 0.9 μm to obtain adsorption print PR11. Similarly, the film thickness was changed as shown in Tables 3 and 4 to obtain adsorption prints PR32 to PR33, respectively.

[0128] Comparative Example 4 A print PR34 was obtained in the same manner as in Example 11, except that the adsorption ink G1 in Example 1 was changed to ink H1.

[0129] (Comparative Example 5) A print PR35 was obtained in the same manner as in Example 18, except that the adsorption ink G8 in Example 8 was changed to ink H2.

[0130] (Comparative Examples 6 and 7) A print PR36 was obtained in the same manner as in Example 19, except that the adsorption ink G9 in Example 9 was changed to ink H3.

[0131] (Comparative Example 8) A printed matter PR37 was obtained in the same manner as in Example 22, except that the adsorption ink G9 in Example 9 was changed to ink H3.

[0132] (Comparative Examples 9, 11, 13, 15, 17, 19, 21, 23 and 25) As in Example 11, adsorption print PR38 was obtained using adsorption ink G1 and changing the film thickness to 0.05 μm as shown in Table 5. Similarly, as shown in Table 5, the adsorption ink and substrate were changed to obtain prints PR40, PR42, PR44, PR46, PR48, PR50, PR52, and PR54, respectively.

[0133] (Comparative Examples 10, 12, 14, 16, 18, 20, 22, 24 and 26) As in Example 11, adsorption print PR39 was obtained using adsorption ink G1 and changing the film thickness to 6.0 μm as shown in Table 5. Similarly, as shown in Table 5, the adsorption ink and substrate were changed to obtain prints PR41, PR43, PR45, PR47, PR49, PR51, PR53, and PR55, respectively.

[0134] The adsorption properties and blocking resistance of the adsorption prints PR1 to PR33 and prints PR34 to PR55 were evaluated, and the results are shown in Tables 3 to 5. If the blocking resistance is poor, ink peeling occurs and the condition of the printed surface deteriorates, making it difficult to use in laminates.

[0135] <Adsorption of printed matter> A 10 cm x 10 cm sample piece was cut from the printed material and placed in a polyvinyl fluoride bag with a rubber stopper. The bag was then heat-sealed. 3 L of air was then inserted through the rubber stopper, and test gas (ammonia) was added to a gas concentration of 100 ppm. The bag was then left to stand at room temperature. The gas concentration inside the bag was measured using a detector tube through the rubber stopper at set intervals (10 min, 1 h, 3 h, 6 h, and 24 h). Measurement was terminated when the gas concentration fell below the lower limit of quantification (1 ppm). A blank test was also conducted, in which the same procedure was repeated without the sample. The gas concentration measurements after 24 hours were compared to evaluate adsorption. The gas concentration after 24 hours was also recorded as the 24-hour gas concentration for samples that had fallen below the lower limit of quantification and were terminated before 24 hours. The lower the gas concentration after 24 hours, the better the adsorption was determined to be. The evaluation was made on a two-point scale: Good: Gas concentration after 24 hours was less than 100 ppm; Bad: Gas concentration after 24 hours remained at 100 ppm.

[0136] <Blocking resistance> The printed material was cut into 3cm x 3cm pieces, the printed side and the non-printed side were placed together, and the pieces were then subjected to a 500g / cm2 test at 50°C for 24 hours. 2 After applying a load of 1000kJ / s, the overlapping portion of the printed and non-printed surfaces was peeled away, and the state of ink peeling was observed, and the peel resistance at that time was evaluated. Those that showed no ink peeling or peel resistance were judged to have good blocking resistance. Ink peeling and peel resistance were evaluated on a three-point scale: ○: no ink peeling or peel resistance, △: slight ink peeling observed, with peel resistance (no practical problems), ×: ink peeling observed throughout, with considerable peel resistance.

[0137] [Laminate fabrication] Impact-resistant polystyrene resin E640N (abbreviated as HIPS, manufactured by Toyo Polystyrene Co., Ltd.) was melt-extruded onto the adsorption ink layer of the adsorption printed matter PR1 using an extrusion laminator at a line speed of 100 m / min and laminated to a thickness of 200 μm to obtain a PR1 / / HIPS laminate LAM1.

[0138] Similarly, the adsorption printed matter PR1 was replaced with adsorption printed matters PR2 to PR4, PR12 to PR19, and printed matters PR34, PR38, and PR40 to obtain laminates LAM2 to LAM4, LAM13 to LAM20, LAM41, and LAM46 to LAM47.

[0139] The absorbent ink layer of the absorbent printed material PR5 was subjected to a corona treatment, and low-density polyethylene resin Petrothene LW01 (abbreviated as LDPE20, manufactured by Tosoh Corporation) was melt-extruded and laminated to a thickness of 20 μm to obtain a PR5 / / LDPE20 laminate LAM5. (" / / " indicates extrusion lamination.) Similarly, the adsorption printed matter PR5 was replaced with adsorption printed matters PR6, PR20-PR23, and printed matters PR42 and PR44 to obtain laminates LAM6, LAM21-LAM24, and LAM48-LAM49. Furthermore, the adsorption printed matters PR5-PR6, PR20-PR23, and printed matters PR42 and PR44 were not extrusion laminated like LAM5, and were designated LAM35-LAM40 and LAM55-LAM56, respectively.

[0140] Similarly, instead of the adsorption printed material PR1, the adsorption printed material PR7 was coated with Takelac A-969V / A-5 (manufactured by Mitsui Chemicals, Inc.) using A-Bar OSP-10 (manufactured by OSG System Products, Inc.), and a 40 μm thick unstretched polyethylene film, Rix L-4102 (abbreviation: LLDPE, manufactured by Toyobo Co., Ltd.), was laminated, followed by aging at 40°C for 24 hours to obtain a PR7 / DL / LLDPE laminate LAM7. Similarly, by replacing the adsorption printed matter PR7 with adsorption printed matters PR8 to PR10, PR24 to PR31 and printed matters PR35 to PR36, PR46, PR48, PR50 and PR52, laminates LAM8 to 9, LAM11, LAM25 to LAM32, LAM42 to 43 and LAM50 to LAM53 were obtained.

[0141] Similarly, instead of the adsorption printed material PR1, the adsorption printed material PR9 was coated with Takelac A-525 / Takenate A-52 (manufactured by Mitsui Chemicals, Inc.) and A-Bar OSP-10 (manufactured by OSG System Products, Inc.), and a 60 μm thick unstretched polypropylene film, Torayfan NO ZK93KM (abbreviated as Reto CPP, manufactured by Toray Film Processing Co., Ltd.), was then laminated, and the resultant was aged at 40°C for 24 hours to obtain a PR9 / DL / Reto CPP laminate LAM10. Similarly, the adsorption printed matter PR9 was replaced with the printed matter PR36 to obtain a laminate LAM44.

[0142] Similarly, instead of the adsorption printed material PR1, the adsorption printed material PR11 was replaced with Takelac A-969V / A-5 (abbreviation: DL, manufactured by Mitsui Chemicals, Inc.) coated with A-Bar OSP-10 (manufactured by OSG System Products, Inc.), and a 30 μm thick unstretched polypropylene film, Pylen P-1128 (abbreviation: CPP, manufactured by Toyobo Co., Ltd.), was laminated, followed by aging at 40°C for 24 hours to obtain a PR11 / DL / CPP laminate LAM12. Similarly, the adsorption printed matter PR11 was replaced with the adsorption printed matters PR32 to PR33 and the printed matters PR37 and PR54 to obtain laminates LAM33 to LAM34, LAM45 and LAM54.

[0143] The adsorptivity of the laminates LAM1 to LAM56 was evaluated and the results are shown in Tables 3 to 5.

[0144] <Adsorption of laminate> A 10 cm x 10 cm sample piece was cut from the laminate and placed in a polyvinyl fluoride bag with a rubber stopper. The bag was then heat-sealed, and 3 L of air was then inserted through the rubber stopper. Test gas (ammonia) was then added to a gas concentration of 100 ppm. The bag was then left to stand at room temperature. The gas concentration inside the bag was measured using a detector tube through the rubber stopper at set intervals (10 min, 1 h, 3 h, 6 h, and 24 h). Measurement was terminated when the gas concentration fell below the lower limit of quantification (1 ppm). A blank test was also conducted, in which the same procedure was repeated without the sample. The gas concentration measurements after 24 hours were compared to evaluate adsorption. The gas concentration after 24 hours was also recorded for samples that had fallen below the lower limit of quantification and were terminated before 24 hours. The lower the gas concentration after 24 hours, the better the adsorption was determined. The evaluation was made on a two-point scale: Good: Gas concentration after 24 hours was less than 100 ppm; Bad: Gas concentration after 24 hours remained at 100 ppm.

[0145] [Table 3]

[0146] [Table 4]

[0147] [Table 5]

[0148] Tables 3 to 5 clearly show that the adsorption inks G1 to G10 of Examples 1 to 10 have better adsorption properties than the results of Examples 11 to 50. Furthermore, it is clear that the adsorption prints PR1 to PR33 have good blocking resistance. It is clear that ink H1 of Comparative Example 1, which uses a copolymer that does not have an A block having a structural unit derived from a (meth)acrylic vinyl monomer represented by general formula (1) and a B block having a structural unit represented by general formula (2), does not exhibit any adsorption effects. It is also clear that ink H2 of Comparative Example 2, which uses a chloride-vinyl acetate copolymer that is not an acid-modified chloride-vinyl acetate copolymer, and ink H3 of Comparative Example 3, which uses a urethane resin that is not a carboxyl group-containing urethane resin, do not exhibit any adsorption effects. It is clear that even when using the adsorption inks of the present invention, the adsorption effects are not exhibited when the print film thickness is smaller than the appropriate range (PR38, PR40, PR42, PR44, PR46, PR48, PR50, PR52, PR54). On the other hand, if the printing film thickness is large, blocking resistance will be poor, causing ink peeling and deteriorating the condition of the printed surface. Although there may be some adsorption effect, it is clear that it will be difficult to use the printed materials (PR39, PR41, PR43, PR45, PR47, PR49, PR51, PR53, PR55) in laminates. Therefore, in addition to being able to suppress unpleasant ammonia-based compound odors that occur in living environments, such as the fishy smell of meat products such as meat and seafood, the putrid odor that occurs when these products rot, the smell of food waste, the excretory odor of toilets, cigarette smoke, and body odor, it is also possible to produce printed materials and laminates that are suitable for printing using a simple printing process.

Claims

1. A gravure ink composition for adsorbing ammonia-based compounds, which is used for an ammonia-based compound-adsorbing printed matter having a substrate and an ammonia-based compound-adsorbing layer having a thickness of 0.1 to 5 μm on at least one of the substrates, The gravure ink composition for adsorbing ammonia-based compounds comprises an acidic group-containing thermoplastic resin (A) and a solvent (B), The acidic group-containing thermoplastic resin (A) is the polymer is at least one of an acrylic resin obtained by copolymerizing at least one of a (meth)acrylic acid ester having a hydrocarbon chain, a (meth)acrylic acid ester having a hydroxyl group, a (meth)acrylic acid ester having an amino group, a (meth)acrylic acid ester having a sulfonic group, a (meth)acrylic acid ester having a phosphoric acid group, and a (meth)acrylic acid ester having a carboxyl group with at least one of (meth)acrylic acid, a (meth)acrylic acid ester having a carboxyl group, a (meth)acrylic acid ester having a sulfonic acid group, and a (meth)acrylic acid ester having a phosphoric acid group; a styrene-unsaturated carboxylic acid copolymer; a rosin-based resin; an acid-modified chloride-vinyl acetate copolymer; and a methacrylic acid homopolymer; The solvent (B) at least one of aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, ester solvents, ketone solvents, glycol ether solvents, and esterified products thereof; The substrate is A gravure ink composition for adsorbing ammonia-based compounds, characterized in that the substrate is at least one of paper, PET film, polyethylene film, polypropylene film, polyamide film, coating film, transparent vapor-deposited polyester film or transparent vapor-deposited polyamide film, and co-extruded film.

2. A gravure ink composition for adsorbing ammonia-based compounds, used for an ammonia-based compound adsorbing printed matter comprising a substrate and an ammonia-based compound adsorption layer having a film thickness of 0.1 to 5 μm on at least one side of the substrate, The gravure ink composition for adsorbing ammonia-based compounds contains, when the total weight of the gravure ink composition for adsorbing ammonia-based compounds is 100% by weight, 1 to 99% by weight, calculated as a solid content, of an acidic group-containing thermoplastic resin (A) and 1 to 99% by weight of a solvent (B); The acidic group-containing thermoplastic resin (A) is the polymer is at least one of an acrylic resin obtained by copolymerizing at least one of a (meth)acrylic acid ester having a hydrocarbon chain, a (meth)acrylic acid ester having a hydroxyl group, a (meth)acrylic acid ester having an amino group, a (meth)acrylic acid ester having a sulfonic group, a (meth)acrylic acid ester having a phosphoric acid group, and a (meth)acrylic acid ester having a carboxyl group with at least one of (meth)acrylic acid, a (meth)acrylic acid ester having a carboxyl group, a (meth)acrylic acid ester having a sulfonic acid group, and a (meth)acrylic acid ester having a phosphoric acid group; a styrene-unsaturated carboxylic acid copolymer; a rosin-based resin; an acid-modified chloride-vinyl acetate copolymer; and a methacrylic acid homopolymer; The solvent (B) at least one of aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, ester solvents, ketone solvents, glycol ether solvents, and esterified products thereof; The substrate is A gravure ink composition for adsorbing ammonia-based compounds, characterized in that the substrate is at least one of paper, PET film, polyethylene film, polypropylene film, polyamide film, coating film, transparent vapor-deposited polyester film or transparent vapor-deposited polyamide film, and co-extruded film.

3. The gravure ink composition for adsorbing ammonia-based compounds according to claim 1 or 2 is laminated on at least one surface of a substrate to form an ammonia-based compound adsorption layer having an ink layer thickness of 0.1 to 5 μm, The substrate is 1. A printed matter for adsorbing an ammonia-based compound, which is made of at least one of paper, PET film, polyethylene film, polypropylene film, polyamide film, coating film, transparent vapor-deposited polyester film or transparent vapor-deposited polyamide film, and co-extruded film.

4. The gravure ink composition for adsorbing ammonia-based compounds according to claim 1 or 2 comprises an ammonia-based compound adsorption layer formed on at least one surface of a substrate, the ammonia-based compound adsorption layer being an ink layer having a thickness of 0.1 to 5 μm, and a laminate layer or a pressure-sensitive adhesive layer being laminated on the ammonia-based compound adsorption layer or on the substrate on the opposite side of the ammonia-based compound adsorption layer, The substrate is A laminate comprising at least one of paper, PET film, polyethylene film, polypropylene film, polyamide film, coating film, transparent vapor-deposited polyester film, transparent vapor-deposited polyamide film, and coextruded film.

5. 5. The laminate according to claim 4, wherein the laminate layer is a sealant layer or a sealing layer.

6. 6. The laminate according to claim 4, wherein the laminate layer is at least one of a dry laminate, a non-solvent laminate, a thermal laminate, an extrusion laminate, a co-extrusion laminate, and a PE sandwich laminate.

7. providing a substrate; a gravure printing step of printing the gravure ink composition for adsorbing ammonia-based compounds according to claim 1 or 2 on at least one of the substrates to form an ink layer with a thickness of 0.1 to 5 μm to form an ammonia-based compound adsorption layer, The substrate is A method for producing a printed matter that adsorbs an ammonia-based compound, characterized in that the printed matter is at least one of paper, PET film, polyethylene film, polypropylene film, polyamide film, coating film, transparent vapor-deposited polyester film or transparent vapor-deposited polyamide film, and co-extruded film.

8. providing a substrate; a gravure printing step of printing the gravure ink composition for adsorbing ammonia-based compounds according to claim 1 or 2 on at least one of the substrates to a film thickness of 0.1 to 5 μm to form an ammonia-based compound adsorption layer; a laminating step or a coating step of forming a laminate layer or a pressure-sensitive adhesive layer on the ammonia-based compound adsorption layer or on the substrate on the opposite side of the ammonia-based compound adsorption layer; Including, The substrate is A method for producing a laminate, characterized in that the laminate is at least one of paper, PET film, polyethylene film, polypropylene film, polyamide film, coating film, transparent vapor-deposited polyester film or transparent vapor-deposited polyamide film, and co-extruded film.

9. 9. The method for producing a laminate according to claim 8, wherein the laminating step is a laminating step for forming a sealant layer, or the coating step is a coating step for forming a sealing layer or a pressure-sensitive adhesive layer.

10. 10. The method for producing a laminate according to claim 8 or 9, wherein the lamination step is a lamination step for forming at least one laminate layer selected from the group consisting of a dry lamination step, a non-solvent lamination step, a thermal lamination step, an extrusion lamination step, a co-extrusion lamination step, and a PE sandwich lamination step.

11. A packaging bag essentially comprising a substrate, an ammonia-based compound-adsorption layer laminated to a thickness of 0.1 to 5 μm, and a sealant layer or a sealing layer, wherein the ammonia-based compound-adsorption layer is formed from the gravure ink composition for adsorbing ammonia-based compounds according to claim 1 or 2, The substrate is A packaging bag characterized by being made of at least one material selected from the group consisting of paper, PET film, polyethylene film, polypropylene film, polyamide film, coating film, transparent vapor-deposited polyester film, transparent vapor-deposited polyamide film, and co-extruded film.

12. A packaging container essentially comprising a substrate, an ammonia-based compound-adsorption layer laminated to a thickness of 0.1 to 5 μm, and an extrusion laminate layer, wherein the ammonia-based compound-adsorption layer is formed from the gravure ink composition for adsorbing ammonia-based compounds according to claim 1 or 2, The substrate is A packaging container characterized by being made of at least one material selected from the group consisting of paper, PET film, polyethylene film, polypropylene film, polyamide film, coating film, transparent vapor-deposited polyester film, transparent vapor-deposited polyamide film, and co-extruded film.

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