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

Abstract

To provide a gravure ink composition for adsorbing aldehyde-based compounds, which can suppress: odors derived from unsaturated aliphatic acids and amino-acids included in meat products such as seafood, seeds, and grains; and aldehydes such as formaldehyde, acetaldehyde, and the like which evaporate from materials used for architectural structures, furniture, and the like, and which, in addition, enables preparation of printed matter having printability by a simple process.SOLUTION: Provided is a gravure ink composition for adsorbing aldehyde-based compounds, comprising: a compound containing at least one selected from primary amino groups, secondary amino groups, and tertiary amino groups; at least one resin of urethane resins, (meth)acrylic resins, polyamide resins, nitrocellulose, chlorinated polyolefin resins, and vinyl chloride-vinyl acetate copolymer resins; and a solvent.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an ink composition that suppresses the unpleasant odor of aldehyde compounds that is generated when ingredients containing unsaturated fatty acids or amino acids, such as fish and shellfish, seeds, and grains, are processed or cooked.The present invention relates to an ink composition that suppresses the odor of aldehyde compounds, such as formaldehyde and acetaldehyde, that volatilize from materials used in buildings and furniture (indoor floors, walls, ceilings, plywood and vinyl walls used in furniture, etc.). [Background technology]

[0002] When processed or cooked, unsaturated fatty acids and amino acids contained in seafood and other meat products, seeds, and grains are oxidized and decomposed into aldehydes, dienals, ketones, and lower fatty acids via peroxides, and aldehydes and the like emit a characteristic fishy odor. These odors are caused by aldehydes such as propanal, 3-methylbutanal, 2-methylpropanal, pentanal, hexanal, octanal, nonanal, decanal, hexenal, heptenal, octenal, nonenal, decenal, benzaldehyde, acetaldehyde, phenylacetaldehyde, methional, hexadecenal, heptadecenal, heptadienal, nonadienal, decadienal, heptadecenal, and methylacetaldehyde. They are derived from dienals such as xadecadienal, trienals such as heptadecatrienal, and ketones such as butanone, pentanone, hexanone, heptanone, octanone, nonanone, undecanone, tridecanone, 3-hydroxy-2-butanone, methylhexanone, methylheptenone, 2,3-butanedione, 2,3-pentanedione, cyclohexanone, acetophenone, aminoacetophenone, and benzophenone. In addition, the effects of aldehydes such as formaldehyde and acetaldehyde that evaporate from materials used in buildings and furniture (such as plywood and vinyl walls used in indoor floors, walls, ceilings, and furniture) on the human body are also a problem. In particular, formaldehyde has become a social issue as it causes sick house syndrome.

[0003] Patent Document 1 proposes a covering liner made by dispersing coconut shell activated carbon in an aqueous resin solution and applying it to the liner surface by gravure printing. The covering liner is made to have the ability to adsorb harmful gases (ethylene, ammonia gas, formaldehyde, etc.) in the cardboard box itself, and to maintain the freshness of the packed products such as vegetables, fruits, and flowers. Coconut shell activated carbon is used as a material having the ability to adsorb harmful gases, and is dispersed in an aqueous resin solution, which is then applied to the liner surface by gravure printing. The application to the liner surface is done three times by gravure printing, with the aqueous resin solution containing coconut shell activated carbon being applied as the top coat agent when applied once or twice, and when applied three times, only the aqueous resin solution is applied as the top coat agent, at 20 to 24 g / m2 for each coat. 2 In order to achieve this, the coating amount must be very thick, and the coating process must be repeated, which is troublesome. In addition, since the coating amount is very large, there is a risk that the printability (blocking resistance) will be poor. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Utility Model Registration No. 3124159 Summary of the Invention [Problem to be solved by the invention]

[0005] Therefore, the present invention aims to provide a gravure ink composition for adsorbing aldehyde-based compounds that can suppress odors of aldehydes, dienals, ketones, lower fatty acids, and the like that are decomposed through oxidation and peroxides when unsaturated fatty acids and amino acids contained in meat products such as seafood, seeds, and grains are processed or cooked, as well as aldehydes such as formaldehyde and acetaldehyde that volatilize from materials used in buildings and furniture, and that can produce printed matter having printability in a simple process. [Means for solving the problem]

[0006] The present inventors have found that the above-mentioned problems can be solved by a gravure ink composition for adsorbing aldehyde compounds, which contains a compound containing at least one of a primary amino group, a secondary amino group, and a tertiary amino group, at least one resin selected from the group consisting of a urethane resin, a (meth)acrylic resin, a polyamide resin, soluble nitrocellulose, a chlorinated polyolefin resin, and a vinyl chloride-vinyl acetate copolymer resin, and a solvent, and have thus completed the present invention.

[0007] That is, the present invention provides (1) A gravure ink composition for adsorbing an aldehyde compound, which is used for an aldehyde compound-adsorbing printed matter having a substrate and an aldehyde 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 an aldehyde compound comprises: N,N-dialkylaminoalkyl(meth)acrylate compounds, polyethyleneimine compounds represented by the general formula (3) described below At least one of seed( A gravure ink composition for adsorbing an aldehyde compound, comprising: (A) at least one resin (b1) selected from the group consisting of a urethane resin, a (meth)acrylic resin, a polyamide resin, nitrocellulose, a chlorinated polyolefin resin, and a vinyl chloride-vinyl acetate copolymer resin; and (C) a solvent. (2) The gravure ink composition for adsorbing aldehyde compounds contains at least one kind (A) of an N,N-dialkylaminoalkyl (meth)acrylate compound and a polyethyleneimine compound represented by the general formula (3) described below, at least one resin (b1) of a urethane resin, a (meth)acrylic resin, a polyamide resin, nitrocellulose, a chlorinated polyolefin resin, and a vinyl chloride-vinyl acetate copolymer resin, and another thermoplastic resin (b2), as a thermoplastic resin (B), and a solvent (C), when the total content of the gravure ink composition for adsorbing aldehyde compounds is taken as 100% by weight: The gravure ink composition for adsorbing aldehyde compounds contains 0.5 to 20% by weight of an N,N-dialkylaminoalkyl (meth)acrylate compound, and at least one kind (A) of a polyethyleneimine compound represented by the following general formula (3), a thermoplastic resin (B) containing at least one resin (b1) selected from urethane resin, (meth)acrylic resin, polyamide resin, nitrocellulose, chlorinated polyolefin resin, and vinyl chloride-vinyl acetate copolymer resin, and other thermoplastic resins (b2), the thermoplastic resin being 1 to 30% by weight in terms of solid content; Contains 65 to 98% by weight of a solvent (C) The gravure ink composition for adsorbing aldehyde compounds according to claim 1, (3) An aldehyde-based compound adsorption printed matter, characterized in that the gravure ink composition for adsorbing an aldehyde-based compound according to (1) or (2) forms an aldehyde-based compound adsorption layer on at least one surface of a substrate, the ink layer having a thickness of 0.1 to 5 μm. (4) A laminate comprising an aldehyde compound adsorption layer formed on at least one surface of a substrate by laminating the gravure ink composition for adsorbing an aldehyde compound according to (1) or (2) with a thickness of 0.1 to 5 μm, and a laminate layer or a pressure-sensitive adhesive layer on the aldehyde compound adsorption layer or on the substrate on the opposite surface of the aldehyde compound adsorption layer. (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, co-extrusion laminate, and PE sandwich laminate. (7) preparing a substrate; a gravure printing step of printing the gravure ink composition for adsorbing aldehyde compounds according to (1) or (2) on at least one of the substrates to form an aldehyde compound adsorption layer having a thickness of 0.1 to 5 μm; (8) preparing a substrate; a gravure printing step of forming an aldehyde compound adsorption layer by printing the gravure ink composition for adsorbing an aldehyde compound according to (1) or (2) on at least one of the substrates in a 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 aldehyde compound adsorption layer or on the substrate on the opposite side of the aldehyde compound adsorption layer; A method for producing a laminate, comprising: (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 aldehyde compound-adsorption layer laminated to a thickness of 0.1 to 5 μm, and a sealant layer or a sealing layer, the packaging bag being characterized in that the aldehyde compound-adsorption layer is formed from the gravure ink composition for adsorbing aldehyde compounds according to (1) or (2). (12) A packaging container essentially comprising a substrate, an aldehyde compound-adsorption layer laminated to a thickness of 0.1 to 5 μm, and an extrusion laminate layer, characterized in that the aldehyde compound-adsorption layer is formed from the gravure ink composition for adsorbing aldehyde compounds according to (1) or (2). This is regarding. Effect of the Invention

[0008] According to the present invention, when unsaturated fatty acids and amino acids contained in meat products such as seafood, seeds, and grains are processed or cooked, they are oxidized to peroxides and decomposed, resulting in the production of odorous aldehydes, dienals, ketones, lower fatty acids, and the like, as well as aldehydes such as formaldehyde and acetaldehyde that volatilize from materials used in buildings and furniture. In addition, a gravure ink composition for adsorbing aldehyde compounds can be provided, which can produce printed matter having printability in a simple process. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] 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.

[0010] In the following description, (meth)acrylic and (meth)acrylate mean acrylic and methacrylic, acrylate and methacrylate, respectively.

[0011] The gravure ink composition for adsorbing aldehyde compounds of the present invention (hereinafter simply referred to as "adsorption ink composition") is used for an aldehyde compound adsorption printed matter having a substrate and an aldehyde compound adsorption layer having a thickness of 0.1 to 5 μm on at least one side of the substrate, and the gravure ink composition for adsorbing aldehyde compounds preferably contains a compound (A) containing at least one of a primary amino group, a secondary amino group, and a tertiary amino group, at least one resin (b1) selected from a urethane resin, a (meth)acrylic resin, a polyamide resin, soluble nitrocellulose, a chlorinated polyolefin resin, and a vinyl chloride-vinyl acetate copolymer resin, and a solvent (C).

[0012] The gravure ink composition for adsorbing aldehyde compounds of the present invention preferably contains a compound (A) containing at least one of a primary amino group, a secondary amino group, and a tertiary amino group. The compound (A) containing at least one of a primary amino group, a secondary amino group, and a tertiary amino group has a primary amino group, a secondary amino group, and a tertiary amino group in its structure that reacts with an aldehyde group or the like to form a bond. As a result, odor can be reduced and aldehydes can be suppressed.

[0013] The compound (A) containing at least one of a primary amino group, a secondary amino group, and a tertiary amino group is more preferably at least one of an N,N-dialkylaminoalkyl (meth)acrylate compound, a polyethyleneimine compound, a modified polyethyleneimine compound, a hydrazine compound, and a urea compound.

[0014] The N,N-dialkylaminoalkyl(meth)acrylate compound includes a compound represented by the following general formula (1).

[0015] [ka] [In formula (1), X 1 and X 2 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms; R 1 represents a linear or branched alkylene group having 2 to 18 carbon atoms, and A represents a (meth)acrylic group represented by general formula (2).

[0016] The compound represented by the general formula (1) is 1 and X 2 are each independently preferably a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and further preferably a linear or branched alkyl group having 1 to 4 carbon atoms. If the number of carbon atoms exceeds 18, the reactivity becomes poor, which is not preferred.

[0017] In formula (1), R 1 is preferably a linear or branched alkylene group having 2 to 18 carbon atoms, more preferably a linear or branched alkylene group having 2 to 10 carbon atoms, and further preferably a linear or branched alkylene group having 2 to 4 carbon atoms. If the number of carbon atoms exceeds 18, the reactivity becomes poor, which is not preferred.

[0018] In formula (1), A represents a (meth)acrylic group represented by the following general formula (2).

[0019] [ka] [In formula (2), R 2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0020] In formula (2), R 2 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably an alkyl group having 1 to 2 carbon atoms.

[0021] Specific examples of the compound represented by the general formula (1) include 2-(dimethylamino)ethyl methacrylate, 2-(diethylamino)ethyl methacrylate, 2-(dimethylamino)ethyl acrylate, 2-(dibutylamino)ethyl acrylate, 2-(butylethylamino)ethyl acrylate, 2-(dimethylamino)-1-methylethyl acrylate, 2-(dimethylamino)-2-methylpropyl acrylate, 2-(diethylamino)-1-methylethyl acrylate, 2-(diisopropylamino)ethyl methacrylate, 3-(dipropylamino)ethyl ... Examples of the methacrylate include Nt-butylaminoethyl acrylate, 2-(dibutylamino)propyl acrylate, 3-(diethylamino)propyl acrylate, Nt-butylaminoethyl acrylate, 2-(dibutylamino)propyl acrylate, 3-(dibutylamino)propyl acrylate, 2-(diethylamino)-1-methylethyl acrylate, 2-(dimethylamino)-2-methylpropyl acrylate, and 2-(cyclohexylamino)ethyl acrylate. Among these, 2-(dimethylamino)ethyl methacrylate and 2-(diethylamino)ethyl methacrylate are more preferred. These may be used alone or in combination.

[0022] The N,N-dialkylaminoalkyl(meth)acrylate compound is preferably an acrylic resin containing the compound as an acrylic monomer component. The acrylic resin may contain a (meth)acrylate compound having a hydrocarbon chain, a (meth)acrylate compound having a hydroxyl group, or a (meth)acrylate compound having an epoxy group, in addition to the compound contained as an acrylic monomer component.

[0023] Examples of the (meth)acrylate compound 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.

[0024] Examples of the (meth)acrylate compound having a hydroxyl group include 2-hydroxymethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxymethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2-methyl-3-hydroxypropyl acrylate, 2-hydroxy-2-methylpropyl acrylate, and ethyl 1-(hydroxymethyl) Acrylate, methyl 2-(hydroxymethyl)acrylate, 1-methyl-2-(hydroxyethyl)methacrylate, ethyl 2-(hydroxymethyl)acrylate, 2-(hydroxymethyl)propyl acrylate, 2-hydroxy-1-(hydroxymethyl)propyl acrylate, 3-hydroxy-1-(hydroxymethyl)propyl acrylate, 2-hydroxy-1-(hydroxymethyl)propyl methacrylate, 1-methyl-3-(hydroxypropyl)methacrylate, 1-(hydroxymethyl)-2,3-dihydroxypropyl acrylate, 1-(hydroxymethyl)-2,3-dihydroxypropyl methacrylate, 2,2-dimethyl-3-(hydroxypropyl)acrylate, 3-hydroxy-1-(hydroxymethyl)propyl methacrylate, 3,4-dihydroxybutyl acrylate, 2,3-dihydroxybutyl acrylate, 2,3-dihydroxybutyl methacrylate, 2,4-dihydroxybutyl acrylate, 2,4-dihydroxybutyl methacrylate, 3,4-dihydroxybutyl methacrylate, 2,3-Dihydroxy-1-methylpropyl methacrylate, triethylene glycol monoacrylate, triethylene glycol monomethacrylate, pentaerythritol monoacrylate, pentaerythritol methacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dimethylolethane methacrylate, dimethylolpropane methacrylate, trimethylolmethane methacrylate, trimethylolmethane dimethacrylate, trimethylolethane monoacrylate, trimethylolethane methacrylate, trimethylolethane bisacrylate, trimethylol Examples of the acrylate include propane acrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, dimethylolmethane methacrylate, trimethylolethane dimethacrylate, (1-hydroxycyclohexyl)methyl acrylate, 2-hydroxycyclohexyl acrylate, glycerin 1-acrylate, glycerin 2-acrylate, glycerin 2-methacrylate, glycerin 1,2-bisacrylate, glycerin 1,2-bismethacrylate, glycerin 1,3-bisacrylate, and glycerin 1,3-bismethacrylate. Among these, 2-hydroxymethyl methacrylate is more preferable.

[0025] The polyethyleneimine compound includes a compound represented by the following general formula (3).

[0026] [ka] [In formula (3), R 3 and R 4 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or an alkyl group having an alicyclic structure having 6 to 12 carbon atoms; R 5represents a hydrogen atom, a linear alkyl group having 1 to 18 carbon atoms, or an alkyl group having an alicyclic structure having 6 to 12 carbon atoms. m represents an integer of 2 to 6, and n represents an integer of 20 to 3000.]

[0027] In formula (3), R 3 and R 4 are each independently preferably a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or an alkyl group having an alicyclic structure having 6 to 12 carbon atoms, more preferably a linear or branched alkyl group having 1 to 8 carbon atoms, and further preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

[0028] In formula (3), R 5 is preferably a hydrogen atom, a linear alkyl group having 1 to 18 carbon atoms, or an alkyl group having an alicyclic structure having 6 to 12 carbon atoms, more preferably a linear alkyl group having 1 to 10 carbon atoms, and even more preferably a linear alkyl group having 1 to 4 carbon atoms.

[0029] In formula (3), m is preferably an integer of 2 to 6, more preferably an integer of 2 to 4, and even more preferably an integer of 2 to 3. n is preferably an integer of 20 to 3,000, more preferably an integer of 100 to 2,000, and even more preferably an integer of 500 to 1,000.

[0030] These polyethyleneimine compounds may be of one type or of two or more types. Commercially available products include Epomin manufactured by Nippon Shokubai Co., Ltd., Polymin manufactured by BASF Japan Ltd., Saftomer AC-72 manufactured by Mitsubishi Chemical Corporation, and Techno Chemical Co., Ltd.

[0031] The hydrazine compound includes a compound having an N-amino group (N-NH2), and more specifically, a compound having a hydrazide group (CONH-NH2) or a hydrazone group (C=N-NH2). Such hydrazine compounds include mono-substituted hydrazines represented by the following general formula (4), dihydrazines represented by the following general formula (5), dihydrazides represented by the following general formula (6), disemicarbazides represented by the following general formula (7), hydrazono group (=N-NH2)-containing hydrazones represented by the following general formula (8), mono-substituted hydrazono group (=N-NHR)-containing hydrazones represented by the following general formula (9), 12 (R 12 represents an alkyl group or a hydroxyalkyl group.)-containing hydrazones, hydrazino group (-NHNH2)-containing hydrazones represented by the following general formula (10), hydrazide group (-CONH-NH2)-containing hydrazones represented by the following general formula (11), and semicarbazide group (-NHCO-NHNH2)-containing hydrazones represented by the following general formula (12).

[0032] R 6 -NHNH2(4) [In the formula, R 6 represents a hydrogen atom, an alkyl group, or a hydroxyalkyl group. H2NHN-R 7 -NHNH2(5) [In the formula, R 7 represents a single bond, an alkylene group, a cycloalkylene group, an arylene group, or a carbonyl group. H2NHNOC-R 8 -CONHNH2(6) [In the formula, R 8 represents a single bond, an alkylene group, a cycloalkylene group, or an arylene group. H2NHN-CONH-R 9 -NHCO-NHNH2(7) [In the formula, R 9 represents a single bond, an alkylene group, a cycloalkylene group, or an arylene group.

[0033] [ka] [In the formula, R 10 and R 11each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or a heterocyclic group.

[0034] [ka] [In the formula, R 12 R represents an alkyl group or a hydroxyalkyl group. 13 and R 14 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or a heterocyclic group.

[0035] [ka] [In the formula, R 15 R represents an alkylene group, a cycloalkylene group, or an arylene group. 16 and R 17 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or a heterocyclic group.

[0036] [ka] [In the formula, R 18 R represents an alkylene group, a cycloalkylene group, or an arylene group. 19 and R 20 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or a heterocyclic group.

[0037] [ka] [In the formula, R 21 R represents an alkylene group, a cycloalkylene group, or an arylene group. 22 and R 23 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or a heterocyclic group.

[0038] R 6 , R 10 , R 11 , R 12 , R 13 , R 14 , R 16 , R 17 , R 19 , R 20 , R 22 , and R 23 The alkyl group represented by the formula (I) includes linear or branched alkyl groups having 1 to 10 carbon atoms.

[0039] R 6 and R 12 Examples of the hydroxyalkyl group represented by the formula (I) include linear or branched hydroxyalkyl groups having 1 to 10 carbon atoms.

[0040] R 7 , R 8 , R 9 , R 15 , R 18 , and R 21 The alkylene group represented by the following formula (1) includes linear or branched alkylene groups having 1 to 10 carbon atoms.

[0041] R 7 , R 8 , R 9 , R 15 , R 18 , and R 21 Examples of the cycloalkylene group represented by the following formula include cycloalkylene groups having 3 to 8 carbon atoms.

[0042] R 7 , R 8 , R 9 , R 15 , R 18 , and R 21 Examples of the arylene group represented by the formula (I) include arylene groups having 6 to 10 carbon atoms, such as phenylene, tolylene, xylene, and naphthylene.

[0043] R 10 , R 11 , R 13 , R 14, R 16 , R 17 , R 19 , R 20 , R 22 , and R 23 The cycloalkyl group represented by the following formula (1) may be a cycloalkyl group having 3 to 10 carbon atoms.

[0044] R 10 , R 11 , R 13 , R 14 , R 16 , R 17 , R 19 , R 20 , R 22 , and R 23 Examples of the aryl group represented by the following formula include aryl groups having 6 to 14 carbon atoms, such as phenyl and naphthyl.

[0045] R 10 , R 11 , R 13 , R 14 , R 16 , R 17 , R 19 , R 20 , R 22 , and R 23 Examples of the aralkyl group represented by the following formula include aralkyl groups having 7 to 16 carbon atoms, such as benzyl and phenethyl.

[0046] R 10 , R 11 , R 13 , R 14 , R 16 , R 17 , R 19 , R 20 , R 22 , and R 23Examples of the heterocyclic group represented by the formula (I) include heterocyclic groups containing an oxygen atom as a heteroatom (e.g., 5-membered ring groups such as furan and oxazole, 6-membered ring groups such as pyran, and fused ring groups such as benzofuran, xanthene, chroman, and isochroman), heterocyclic groups containing a sulfur atom as a heteroatom (e.g., 5-membered ring groups such as thiophene, thiazole, isothiazole, and thiadiazole), and heterocyclic groups containing a nitrogen atom as a heteroatom (e.g., 5-membered ring groups such as pyrroline, pyrrolidine, imidazoline, pyrrole, pyrazole, and imidazole, 6-membered ring groups such as piperidine, piperazine, morpholine, pyridine, pyridazine, pyrimidine, and pyrazine, and fused ring groups such as indole, indole, isoindole, indazole, indoline, isoindoline, quinoline, isoquinoline, phthalazine, purine, carbazole, acridine, phenanthrozine, and phenanthroline).

[0047] Examples of the urea compound include urea, methyl urea, dimethyl urea, ethyl urea, diethyl urea, ethylene urea, etc. Among these, urea and ethylene urea are more preferable.

[0048] The compound (A) containing at least one of a primary amino group, a secondary amino group, and a tertiary amino group is more preferably 2-(dimethylamino)ethyl methacrylate, 2-(diethylamino)ethyl methacrylate, a polyethyleneimine compound, or urea.

[0049] In the adsorption ink composition of the present invention, the compound (A) containing at least one of the primary amino group, secondary amino group, and tertiary amino group is preferably 0.5 to 20% by weight, more preferably 0.7 to 15% by weight, and even more preferably 1 to 10% by weight. If the content of the compound (A) containing at least one of the primary amino group, secondary amino group, and tertiary amino group is less than 0.5% by weight, the adsorption ink composition has poor adsorption properties for aldehyde compounds, and if the content of the compound (A) containing at least one of the primary amino group, secondary amino group, and tertiary amino group is more than 20% by weight, the adsorption ink composition has poor blocking resistance and poor solubility, which may cause clouding or gelation.

[0050] The gravure ink composition for adsorbing aldehyde compounds of the present invention preferably contains at least one resin (b1) selected from urethane resin, (meth)acrylic resin, polyamide resin, nitrocellulose, chlorinated polyolefin resin, and vinyl chloride-vinyl acetate copolymer resin. The method for preparing these resins may be any conventional method. These resins may be of one type or of two or more types. Commercially available products that can be used include LG-FK R medium (urethane-based), PULPTECC medium (polyamide-based), LRC-LAMI medium (nitrocellulose-based), SYNA-S medium (acrylic-based), NOPL-L medium (chlorinated polyolefin-based), and LAMREK medium (vinyl chloride-acetate-based) (all manufactured by Tokyo Ink Co., Ltd.).

[0051] The gravure ink composition for adsorbing aldehyde compounds of the present invention may contain other thermoplastic resins (b2) in addition to the resin (b1). For example, shellacs, rosins, rosin-modified maleic acid resins, rosin-modified phenolic resins, cellulose acetate, cellulose acetyl propionate, cellulose acetyl butyrate, chlorinated rubber, cyclized rubber, polyethylene resins, polypropylene resins, vinyl chloride-vinyl acetate copolymer resins, vinyl chloride resins, ethylene-(meth)acrylic acid copolymers, polyester resins, polyvinylidene chloride resins, vinyl acetate resins, ketone resins, butyral resins, chlorinated ethylene vinyl acetate resins, ethylene vinyl acetate resins, styrene maleic acid resins, polystyrene resins, etc. Preferred are polyacetal resins, polycarbonate resins, casein, alkyd resins, acrylonitrile resins, acrylonitrile-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, polysulfone resins, polyether resins, polyethersulfone resins, polyetherketone resins, modified polyphenylene ether resins, polyphenylenesulfone resins, polyimide resins, polyamideimide resins, amorphous polyarylate resins, polyetheretherketone resins, polyvinyl alcohol resins, ethylene-vinyl alcohol resins, polylactic acid, etc. These resins may be used alone or in combination of two or more kinds. Commercially available products that can be used include TPH medium, VESTA medium, LRC-NT medium, and KCNT medium (all manufactured by Tokyo Ink Co., Ltd.).

[0052] In the adsorption ink composition of the present invention, the content of the thermoplastic resin (B), which is the sum of the resin (b1) and the other thermoplastic resin (b2), is preferably 1 to 30% by weight, more preferably 3 to 20% by weight, calculated as solid content. If the content of the thermoplastic resin (B) is less than 1% by weight, the film-forming property of the adsorption ink composition is poor, and if the content of the thermoplastic resin (B) is more than 30% by weight, the fluidity of the adsorption ink composition is poor, and the manufacturing suitability is poor.

[0053] The gravure ink composition for adsorbing aldehyde compounds of the present invention can use a solvent that is usually used in gravure inks. Examples of the solvent 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 ... Examples of the glycol ether 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, and esterified products thereof. As the esterified products, acetates are mainly selected, for example, 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 them, from the viewpoint of printability and versatility, toluene, ethyl acetate, n-propyl acetate, isopropyl alcohol, methanol, propylene glycol monomethyl ether, and methyl ethyl ketone are more preferable. These can be used alone or in combination. The solvent in the adsorption ink composition is preferably within the range of 65 to 98% by weight. If it is less than 65% by weight, the solid content will be high, the fluidity will be poor, and the ink manufacturing suitability will be poor, while if it exceeds 98% by weight, the ink film thickness will become locally non-uniform, irregular shading (swim phenomenon) will occur on the printed surface, the viscosity will be low, and the pigment will be more likely to settle.

[0054] The adsorption ink composition may also contain coloring materials, inorganic fillers, organic fillers, defoamers, 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.

[0055] The colorant may include 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 pearls, organic pigments such as phthalocyanine, insoluble azo, condensed azo, dioxazine, anthraquinone, quinacridone, perylene, perinone, thioindigo, 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. As dyes, those that dissolve or disperse in a solvent are preferred, and may be used alone or in combination of two or more. Among them, it is preferable to use pigments from the viewpoint of durability.

[0056] The substrate is preferably at least one selected from paper, plastic film or sheet, and laminates thereof. For example, 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 a barrier layer disposed between them, polycarbonate films, polyacrylonitrile films, polyimide films, cellophane, moisture-proof cellophane, transparent vapor-deposited polyester films or transparent vapor-deposited polyamide films with vapor-deposited layers of alumina, silica, etc. on PET films or polyamide films, various coating films coated with polyvinylidene chloride resin, polyvinyl alcohol resin, polyacrylic acid resin, etc., co-extruded films of PET and nylon, polylactic acid films, polyvinyl chloride, or polyvinyl chloride resin sheets (foamed PVC sheets, foamed PVC boards, hard PVC sheets, soft PVC sheets) such as polymers of vinyl chloride, vinyl chloride-vinyl acetate copolymer, and ethylene-vinyl acetate copolymer. These may be either stretched or unstretched, and one or more types may be laminated. An appropriate one can be selected in consideration of mechanical strength and dimensional stability. In addition, in order to improve the adhesion of the anchor coat layer or the laminate layer, the printed surface may be subjected to corona treatment, low-temperature plasma treatment, frame treatment, solvent treatment, coating treatment, etc., or may be previously subjected to the treatment. Among them, PET film, polyethylene film, polypropylene film, polyamide film, coating film, transparent vapor deposition polyester film or transparent vapor deposition polyamide film, coextrusion film, etc. are preferred. There is no particular restriction on the thickness of the substrate as long as it is within a range that does not interfere with the printability and winding suitability, but in the case of a film, it is preferably 5 to 300 μm, more preferably 6 to 250 μm. In the case of a sheet, it is preferably 50 μm to 5 mm, more preferably 100 μm to 3 mm.Furthermore, when the substrate is a film having heat sealability, such as a polyethylene film, the substrate itself may function as a sealant layer.

[0057] 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 thermoplastic resin or the like by dry lamination, non-solvent lamination, extrusion lamination, or a method of laminating via an adhesive, or may be a suitable combination of these. A laminated body to which heat sealability has been imparted can also be used as the paper substrate. Methods of imparting heat sealability include lamination of a known sealant film, resin coating by extrusion lamination, coating of a heat seal agent or hot melt, and heat sealable resin processing by coextrusion, and the layer to which heat sealability has been imparted by these methods is also called a heat seal layer. The thickness of the paper substrate is not particularly limited as long as it is within a range that does not interfere with printability and winding suitability, but is preferably 5 to 800 μm, more preferably 6 to 600 μm.

[0058] In the aldehyde-based compound adsorption printed matter of the present invention, the gravure ink composition for adsorbing aldehyde-based compounds preferably forms an aldehyde-based compound adsorption layer by laminating an ink layer on at least one surface of a substrate. The thickness of the ink layer is preferably 0.1 to 5 μm, more preferably 0.3 to 3 μm. If it is thinner than 0.1 μm, the adsorption property is reduced. If it is thicker than 5 μm, the blocking resistance is poor.

[0059] The aldehyde compound adsorption layer is preferably formed by laminating an ink layer on at least one surface of a substrate. The aldehyde compound adsorption layer is preferably formed by coating by a gravure printing method. In particular, it is more preferable to form the layer by coating by a gravure printing method using a multi-color gravure printer. The aldehyde compound adsorption layer may be a single ink layer formed by laminating a gravure ink composition for aldehyde compound adsorption, or may include the ink layer and another ink layer formed by laminating another gravure ink composition. Furthermore, since the layer is formed by coating by a gravure printing method, not only full solid printing but also partial printing and reverse printing are possible. Depending on the final laminate form, the position of the substrate for forming the aldehyde compound adsorption layer may change, and the order of formation of the ink layer and other ink layers may change. That is, for example, an aldehyde-based compound adsorption layer may be formed as in substrate / ink layer / other ink layer, and then another substrate may be laminated by dry lamination or the like (substrate / ink layer / other ink layer / DL / other substrate), or an aldehyde-based compound adsorption layer may be formed as in substrate / other ink layer / ink layer (or ink layer / other ink layer, etc., multiple laminates), and then another substrate may be laminated by dry lamination or the like (substrate / other ink layer / ink layer / (other ink layer, etc. / )DL / other substrate). In addition, by using a printing machine having a reversing mechanism, an aldehyde-based compound adsorption printed matter having a variety of other ink layers can be obtained. For example, an aldehyde-based compound adsorption layer may be formed as in substrate / ink layer / other ink layer, and then the reversing is performed to form another ink layer, and then another substrate may be laminated by dry lamination or the like (other substrate / DL / other ink layer / substrate / ink layer / other ink layer / DL / other substrate).

[0060] In addition to the aldehyde compound adsorption layer, the aldehyde 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 properties, light blocking properties, and straight cut properties. When an intermediate layer is provided, it is not necessarily necessary to apply the aldehyde compound adsorption layer to the substrate, and the aldehyde compound adsorption layer may be provided on the intermediate layer. However, it is preferable that the gas barrier layer for imparting gas barrier properties is not provided closer to the source of the adsorbed substance than the aldehyde compound adsorption layer.

[0061] 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 a barrier layer disposed between them; polycarbonate films, polyacrylonitrile films, polyimide films, cellophane, moisture-proof cellophane; transparent vapor-deposited polyester films or transparent vapor-deposited polyamide films in which a vapor-deposited layer of alumina or silica is provided on a PET film or polyamide film; 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 one or more types may be laminated. An appropriate one can be selected in consideration of mechanical strength, dimensional stability, and the like. In order to improve adhesion, the bonding surfaces may be subjected to corona treatment, low-temperature plasma treatment, frame treatment, solvent treatment, coating treatment, etc., or may be previously subjected to such treatment. Both surfaces are preferably treated. The intermediate layer may have any thickness as long as it does not impair printability or windability, and the thickness is preferably from 5 to 300 μm, and more preferably from 6 to 250 μm.

[0062] The laminate of the present invention is preferably formed by laminating an ink layer of the gravure ink composition for adsorbing aldehyde compounds on at least one surface of a substrate to form an aldehyde compound adsorption layer, and laminating a laminate layer or an adhesive layer on the aldehyde compound adsorption layer or on the substrate on the opposite surface of the aldehyde compound adsorption layer. The thickness of the ink layer is preferably 0.1 to 5 μm, more preferably 0.3 to 3 μm. The laminate layer is preferably a layer formed by dry lamination, non-solvent lamination, 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. Furthermore, an adhesive layer or a pressure sensitive adhesive layer may be provided on the substrate on the side opposite to the aldehyde compound adsorptive layer. The laminate layer may be a sealant layer or a sealing layer. The sealant layer may be, for example, a laminate with heat sealability, a known sealant film, or a resin coating by extrusion lamination. The sealing layer may be, for example, a layer formed by coating a heat sealant or hot melt agent. The pressure-sensitive adhesive layer may be, for example, a layer formed by coating an adhesive or pressure-sensitive adhesive.

[0063] As for the sealant layer, the lamination method is appropriately selected according to the substrate, application, configuration, etc., so long as the seal strength can be sufficiently secured. For example, lamination of a known sealant film via an adhesive to the aldehyde compound adsorption layer on the substrate (dry lamination method, non-solvent lamination method, wet lamination method), lamination by heat (thermal lamination method), resin coating by extrusion lamination method (extrusion lamination method, co-extrusion lamination method, PE sandwich lamination method), etc. can be preferably used. The laminate can be manufactured by one of these methods or a combination of them. 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.

[0064] Examples of the sealant film include polyolefin films such as polyethylene, polypropylene, ethylene-vinyl acetate, and copolymers thereof, co-extruded films and colored films thereof, polystyrene films, polyacrylonitrile films, and ethylene-vinyl alcohol resin films. These films may be stretched or unstretched, and one or more types may be laminated.

[0065] When an adhesive is used in the dry lamination method, non-solvent lamination method, wet lamination method, extrusion lamination method, etc., a commercially available adhesive may be used, for example, a two-liquid or one-liquid type urethane resin adhesive, an acrylic type, an epoxy type, a polyester type, a polyethyleneimine type, a polybutadiene type, an aqueous urethane type, an isocyanate type, an organic titanium type, a starch type water-soluble adhesive, or an aqueous adhesive such as a vinyl acetate emulsion. A known application method can be used as a method for applying the adhesive to form a sealant layer, for example, a roll coater, a reverse roll coater, a gravure coater, a microgravure coater, a knife coater, a bar coater, a wire bar coater, a die coater, a dip coater, etc. can be used. The thickness of the adhesive is not particularly limited, but is preferably in the range of about 0.001 to 10 μm, and particularly preferably in the range of 0.01 to 5 μm.

[0066] 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.

[0067] The method of forming the sealing layer is appropriately selected according to the substrate, application, configuration, etc., as long as sufficient sealing strength can be ensured. For example, coating of a heat-sealing agent or hot melt can be preferably used. The laminate can be manufactured by one or a combination of these methods. The thickness of the sealing layer is not particularly limited, but is preferably 1 to 50 μm for coating of a hot-melt adhesive and 0.01 to 30 μm for coating of a heat-sealing agent.

[0068] Examples of the resin of the heat sealant include thermoplastic resins such as vinylidene chloride, shellacs, rosins, rosin-modified maleic acid resins, rosin-modified phenolic resins, nitrocellulose, cellulose acetate, cellulose acetyl propionate, cellulose acetyl butyrate, 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 alone or in combination of two or more. Examples include types in which these resins are dissolved in a solvent, or types dispersed in water such as acrylic emulsions, urethane emulsions, ethylene-vinyl alcohol emulsions, polyethylene emulsions, polypropylene emulsions, and ethylene vinyl acetate emulsions.

[0069] In addition, 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).

[0070] Resins that can be used for resin coating by the extrusion lamination method include 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 thermoplastic resins such as polybutylene terephthalate resins, and these resins may be used alone or in combination.

[0071] The aldehyde compound-adsorbing printed matter of the present invention is preferably used for packaging, food preservation, retort, microwave oven, agriculture, civil engineering, fishing, automobile interior / exterior, marine, daily necessities, building material interior / exterior, housing equipment, medical / medical equipment, pharmaceutical, home appliances, furniture, stationery / office supplies, sales promotion, commercial, electrical / electronic industry, industrial material, etc. Among them, it is more preferably used for packaging, automobile interior / exterior, daily necessities, building material interior / exterior, furniture, stationery / office supplies, and sales promotion.

[0072] The method for producing an aldehyde compound adsorption printed matter of the present invention preferably includes a step of preparing a substrate, and a gravure printing step of forming an aldehyde compound adsorption layer by printing the gravure ink composition for adsorbing aldehyde compounds on at least one of the substrates. The thickness of the aldehyde 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 the aldehyde compound decreases. If it is more than 5 μm, the blocking resistance is poor.

[0073] The method for producing the aldehyde compound adsorption printed matter may be a method for producing an aldehyde compound adsorption layer alone by printing the gravure ink composition for adsorbing aldehyde compounds, or may include a gravure printing step for producing the aldehyde compound adsorption layer and another printed layer by printing another gravure ink composition, and is more preferably produced by a gravure printing step using a multicolor gravure printer. Furthermore, a gravure printer having a reversing mechanism may be used.

[0074] In addition to the aldehyde compound adsorption layer, a step of forming an intermediate layer for imparting or enhancing 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 provided on the source side of the adsorbed substance relative to the aldehyde compound adsorption layer.

[0075] The method for producing the laminate of the present invention preferably includes a step of preparing a substrate, a gravure printing step of forming an aldehyde compound adsorption layer by printing the gravure ink composition for adsorbing aldehyde compounds in a film thickness of 0.1 to 5 μm on at least one side of the substrate, and a lamination step or coating step of forming a laminate layer or a pressure-sensitive adhesive layer on the aldehyde compound adsorption layer or on the substrate on the side opposite to the aldehyde compound adsorption layer, and the lamination step is preferably a lamination step of forming at least one laminate layer selected from 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. Furthermore, an adhesive layer or a pressure sensitive adhesive layer may be provided on the substrate on the side opposite to the aldehyde compound adsorptive 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 seal layer, or the coating step may be a coating step for forming a pressure-sensitive adhesive layer.

[0076] 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 seal agent or a hot melt agent, etc. The coating step for forming the pressure-sensitive adhesive layer may be a step of coating an adhesive or a pressure-sensitive adhesive, etc.

[0077] The packaging bag of the present invention essentially comprises a substrate, an aldehyde-based compound adsorption layer, and a sealant layer or a sealing layer, and it is preferable that the aldehyde-based compound adsorption layer is formed from the gravure ink composition for adsorbing aldehyde-based compounds.

[0078] The packaging bag may be of any known type, such as two-sided sealed, three-sided sealed, four-sided sealed, pillow sealed, standing pouch, envelope sealed, gusseted, or heat-cut sealed.

[0079] The packaging container of the present invention is a packaging container essentially comprising a substrate, an aldehyde-based compound-adsorption layer, and a sealant layer or a sealing layer, and it is preferable that the aldehyde-based compound-adsorption layer is formed from the gravure ink composition for adsorbing aldehyde-based compounds.

[0080] The packaging container may be any of the well-known forms used for packaging purposes, such as cups, trays, bottles, containers, boxes, cases, food containers, covers, lids, caps, labels, and in-mold cups.

[0081] The gravure ink composition for adsorbing aldehyde compounds of the present invention can be produced by a known method by uniformly dissolving or dispersing a compound containing at least one of a primary amino group, a secondary amino group, and a tertiary amino group, a thermoplastic resin, a coloring material, various additives, etc. in a solvent. For dissolving or dispersing, various stirrers or dispersers such as a dissolver, a roll mill, a ball mill, a bead mill, a sand mill, an attritor, a paint shaker, an agitator, a Henschel mixer, a colloid mill, a pearl mill, an ultrasonic homogenizer, a wet jet mill, a kneader, a homomixer, etc. may be used. These devices may be used alone or in combination of two or more. If air bubbles or coarse particles are contained in the adsorption ink composition, they are preferably removed using a known filter or centrifuge, etc., since they reduce printability and print quality.

[0082] The viscosity of the gravure ink composition for adsorbing an aldehyde compound is not particularly limited as long as it does not interfere with printing. In consideration of the manufacturability and handling of the ink composition used in gravure printing, it is preferably 10 to 1,000 mPa·s at 25°C. If it is less than 10 mPa·s, the viscosity is too low and the pigment tends to settle, and if it is more than 1,000 mPa·s, the fluidity is poor, causing problems during ink production and making it difficult to fill the container. In this case, it can be measured using a commercially available viscometer such as a Brookfield viscometer or a cone-plate viscometer.

[0083] The adsorption ink composition is preferably used in gravure printing, and may be applied as is, but may be adjusted to a desired viscosity by diluting with a diluting solvent in a Zahn Cup #3 (manufactured by Rigo Co., Ltd.) depending on the coating conditions and coating effect. In this case, the viscosity is preferably 10 to 40 seconds at 25°C. If it is less than 10 seconds, it tends to swim, and if it is more than 40 seconds, transferability during printing becomes poor.

[0084] The dilution solvent may be any solvent that can adjust the viscosity of the adsorption ink composition, and examples of the dilution solvent include organic solvents. Commercially available solvents are also available, and are not particularly limited. 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.).

[0085] During printing, if necessary, a curing agent can be added to the adsorption ink composition. For example, polyisocyanate-based curing agents such as 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 modified forms such as trimethylolpropane trimer, isocyanurate, biuret, and allophanate can be used alone or in combination of two or more. 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, A201H (manufactured by Asahi Kasei Corporation), Mytech Y260A (manufactured by Mitsubishi Chemical Corporation), Coronate HX, Coronate HL, 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.). EXAMPLES

[0086] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited thereto. In the examples and comparative examples, "parts" means "parts by mass" and "%" means "% by weight."

[0087] [Preparation of gravure ink composition for adsorbing aldehyde compounds] Example 1 An acrylic resin solution A (solid content 40%, weight average molecular weight 40,000) containing an acrylic resin synthesized by a conventional method from 40 parts of methyl methacrylate, 50 parts of 2-(dimethylamino)ethyl methacrylate, and 10 parts of 2-hydroxyethyl methacrylate, and a mixed solvent of isopropyl alcohol / ethyl acetate = 1 / 1 was obtained. 25 parts of the acrylic resin solution A, 50 parts of SYNA-S medium (manufactured by Tokyo Ink Co., Ltd.), 10 parts of n-propyl acetate, and 15 parts of isopropyl alcohol were charged and stirred with a stirrer for 30 minutes to prepare a gravure ink composition for adsorbing aldehyde compounds G1 (abbreviation: adsorption ink G1).

[0088] (Examples 2 to 4) 2-(Dimethylamino)ethyl methacrylate was used instead of 2-(Diethylamino)ethyl methacrylate, and an acrylic resin solution B (solid content 40%, weight average molecular weight 40,000) was obtained in the same manner as in Example 1, and a gravure ink composition G2 for adsorbing aldehyde compounds (abbreviation: adsorption ink G2) was prepared in the same manner as in Example 1. Similarly, the adsorption inks of Examples 3 and 4 were prepared according to the formulations in Table 1.

[0089] (Examples 5 to 11) 60 parts of LG-FK R medium (solid content 20%, manufactured by Tokyo Ink Co., Ltd.), 3 parts of polyethyleneimine (Epomin SP-012, molecular weight 1,200, manufactured by Nippon Shokubai Co., Ltd.), 27 parts of n-propyl acetate, and 10 parts of isopropyl alcohol were charged and stirred for 30 minutes with a stirrer to prepare a gravure ink composition G5 for adsorbing aldehyde compounds (abbreviation: adsorption ink G5). Similarly, the adsorption inks of Examples 6 to 11 were prepared according to the formulations in Table 1.

[0090] Example 12 Two parts of urea (Tokyo Chemical Industry Co., Ltd.), 10 parts of propylene glycol monomethyl ether, and 10 parts of methanol were charged and dissolved by stirring for 30 minutes using a stirrer. Then, 18 parts of propylene glycol monomethyl ether, 10 parts of methyl ethyl ketone, and 50 parts of LG-FK R medium (solid content 20%, Tokyo Ink Co., Ltd.) were added and the mixture was further stirred for 30 minutes using a stirrer to prepare gravure ink composition for adsorbing aldehyde compounds G12 (abbreviation: adsorption ink G12).

[0091] Example 13 50 parts of LG-FK R medium (solid content 20%, manufactured by Tokyo Ink Co., Ltd.), 3 parts of polyethyleneimine (Epomin SP-012, molecular weight 1,200, manufactured by Nippon Shokubai Co., Ltd.), 20 parts of titanium dioxide (CI Pigment White 7), 22 parts of n-propyl acetate, and 5 parts of isopropyl alcohol were mixed and stirred, and then dispersed using a paint shaker to prepare gravure ink composition for adsorbing aldehyde compounds G13 (abbreviation: adsorption ink G13).

[0092] Comparative Example 1 An acrylic resin solution C (solid content 40%, weight average molecular weight 50,000) containing an acrylic resin synthesized by a conventional method from 35 parts of methyl methacrylate and 65 parts of butyl methacrylate and a mixed solvent of isopropyl alcohol / ethyl acetate = 1 / 1 was obtained, and 25 parts of the acrylic resin solution C, 50 parts of SYNA-S medium (manufactured by Tokyo Ink Co., Ltd.), 10 parts of n-propyl acetate, and 15 parts of isopropyl alcohol were charged and stirred for 30 minutes with a stirrer to prepare a gravure ink composition for adsorbing aldehyde compounds G14 (abbreviation: adsorption ink G14).

[0093] [Table 1]

[0094] [Preparation of printed matter adsorbing aldehyde compounds] (Examples 14 to 17) 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 of Example 1 was adjusted to a viscosity of 17 seconds using a Zahn cup No. 3 with a dilution solvent (40 parts MEK, 40 parts propyl acetate, 20 parts isopropyl alcohol), and then printed at a film thickness of 1.0 μm on a 18 μm-thick unstretched polystyrene film, Styrophane SPH (abbreviation: CPS, manufactured by Oishi Sangyo Co., Ltd.), to obtain an adsorption print PR1. Similarly, the adsorption ink and film thickness were changed as shown in Table 2, and adsorption prints PR2 to PR4 were obtained, respectively.

[0095] (Examples 18, 28 to 32 and 43 to 48) Furthermore, the substrate was changed to a 20 μm-thick stretched polypropylene film, Pylen P-2161 (abbreviation: OPP, manufactured by Toyobo Co., Ltd.), and the adsorption ink G5 was printed at a film thickness of 1.0 μm to obtain the adsorption print PR5. Similarly, the adsorption ink and film thickness were changed as shown in Table 2 to obtain the adsorption prints PR14 to PR18 and PR29 to PR34, respectively.

[0096] (Example 19) Furthermore, the substrate was replaced with a 12 μm-thick polyethylene terephthalate film E-5102 (abbreviation: PET, manufactured by Toyobo Co., Ltd.), and the adsorption ink G5 was printed in a film thickness of 1.1 μm to obtain an adsorption print PR6.

[0097] Example 21 Furthermore, the substrate was replaced with Emblem ON-RT (abbreviation: NY, manufactured by Unitika Ltd.) made of a 15 μm-thick nylon film, and the adsorption ink G5 was printed at a film thickness of 1.1 μm to obtain an adsorption print PR7.

[0098] Example 22 Furthermore, the substrate was replaced with a 12 μm thick vapor-deposited polyethylene terephthalate film, Barrilox 1011HGCR (abbreviation: vapor-deposited PET, manufactured by Toray Film Processing Co., Ltd.), and the adsorption ink G5 was printed at a film thickness of 1.0 μm to obtain an adsorption print PR8.

[0099] (Examples 23 and 33-34) Furthermore, the substrate was replaced with a 40 μm-thick unstretched linear low-density polyethylene film L-4102 (abbreviation: PE, manufactured by Toyobo Co., Ltd.), and the adsorption ink G6 was printed at a film thickness of 1.0 μm to obtain the adsorption print PR9. Similarly, the film thickness was changed as shown in Table 2 to obtain the adsorption prints PR19 to PR20, respectively.

[0100] (Examples 24 and 35 to 36) Furthermore, the base material is 50 g / m 2 Instead of the gravure paper, one-sided gloss bleached kraft paper (abbreviation: paper, manufactured by Oji Materia Co., Ltd.), the adsorption ink G7 was printed at a film thickness of 1.1 μm to obtain the adsorption print PR10. Similarly, the film thickness was changed as shown in Table 2 to obtain the adsorption prints PR21 to PR22.

[0101] (Examples 25 and 37 to 38) Furthermore, the substrate was replaced with Styrophane SPH (abbreviation: CPS, manufactured by Oishi Sangyo Co., Ltd.), a non-oriented polystyrene film with a thickness of 18 μm, and the adsorption ink G8 was printed with a film thickness of 1.0 μm to obtain the adsorption print PR11. Similarly, the film thickness was changed as shown in Table 2 to obtain the adsorption print PR23 to PR24.

[0102] (Examples 26 and 39-40) Furthermore, the substrate was replaced with a 25 μm-thick unstretched polypropylene film KT (abbreviation: CPP, manufactured by Sun-Tox Co., Ltd.), and the adsorption ink G9 was printed at a film thickness of 0.9 μm to obtain an adsorption print PR12. Similarly, the film thickness was changed as shown in Table 2 to obtain adsorption prints PR25 to PR26, respectively.

[0103] (Examples 27 and 41-42) Furthermore, the substrate was replaced with a 12 μm thick polyethylene terephthalate film E-5102 (abbreviation: PET, manufactured by Toyobo Co., Ltd.), and the adsorption ink G10 was printed at a film thickness of 1.1 μm to obtain an adsorption print PR13. Similarly, the film thickness was changed as shown in Table 2 to obtain adsorption prints PR27 to PR28, respectively.

[0104] Comparative Example 2 The adsorption ink G1 in Example 1 was changed to the adsorption ink 14, and the same procedure as in Example 14 was followed to obtain an adsorption printed matter PR35.

[0105] Comparative Example 3 The LG-FK R medium used in Example 5 was adjusted to a viscosity of 17 seconds using a Zahn cup No. 3 with a dilution solvent (40 parts MEK, 40 parts propyl acetate, 20 parts isopropyl alcohol), and then printed to a film thickness of 0.9 μm on a 20 μm-thick stretched polypropylene film, Pylen P-2161 (abbreviation: OPP, manufactured by Toyobo Co., Ltd.) to obtain an adsorption print PR36.

[0106] Comparative Example 4 Furthermore, the substrate was changed to a 12 μm-thick polyethylene terephthalate film E-5102 (abbreviation: PET, manufactured by Toyobo Co., Ltd.), and printing was performed in a film thickness of 1.0 μm in the same manner as in Comparative Example 3 to obtain an adsorption print PR37.

[0107] Comparative Example 6 Furthermore, the substrate was changed to a 15 μm-thick nylon film Emblem ON-RT (abbreviation: NY, manufactured by Unitika Ltd.), and printing was performed in a film thickness of 0.9 μm in the same manner as in Comparative Example 3 to obtain an adsorption print PR38.

[0108] Comparative Example 7 Furthermore, the substrate was changed to a 12 μm thick vapor-deposited polyethylene terephthalate film, Barrilox 1011HGCR (abbreviation: vapor-deposited PET, manufactured by Toray Film Processing Co., Ltd.), and printing was performed with a film thickness of 1.0 μm in the same manner as in Comparative Example 3 to obtain an adsorption print PR39.

[0109] Comparative Example 7 Furthermore, the substrate was changed to a 40 μm-thick unstretched linear low-density polyethylene film L-4102 (abbreviation: PE, manufactured by Toyobo Co., Ltd.), and the PULPTECC medium used in Example 6 was adjusted to a viscosity of 17 seconds using a Zahn cup No. 3 with a dilution solvent (40 parts MEK, 40 parts propyl acetate, 20 parts isopropyl alcohol), and then printed at a film thickness of 1.1 μm to obtain an adsorption print PR40.

[0110] Comparative Example 9 Furthermore, the base material is 50 g / m 2 Instead of the gravure paper, one-sided gloss bleached kraft paper (abbreviation: paper, manufactured by Oji Materia Co., Ltd.), the LRC-LAMI medium used in Example 7 was adjusted to a viscosity of 17 seconds using a Zahn cup No. 3 with a dilution solvent (40 parts MEK, 40 parts propyl acetate, 20 parts isopropyl alcohol), and then printed at a film thickness of 1.0 μm to obtain an adsorption print PR41.

[0111] Comparative Example 10 Furthermore, the substrate was changed to Styrophane SPH (abbreviation: CPS, manufactured by Oishi Sangyo Co., Ltd.), an unstretched polystyrene film with a thickness of 18 μm, and the SYNA-S medium used in Example 8 was adjusted to a viscosity of 17 seconds using a Zahn cup No. 3 with a dilution solvent (40 parts MEK, 40 parts propyl acetate, 20 parts isopropyl alcohol), and then printed at a film thickness of 0.9 μm to obtain an adsorption print PR42.

[0112] Comparative Example 11 Furthermore, the substrate was changed to a 25 μm-thick unoriented polypropylene film KT (abbreviation: CPP, manufactured by Sun-Tox Co., Ltd.), and the NOPL-L medium used in Example 9 was adjusted to a viscosity of 17 seconds using a Zahn cup No. 3 with a dilution solvent (40 parts MEK, 40 parts propyl acetate, 20 parts isopropyl alcohol), and then printed at a film thickness of 1.0 μm to obtain an adsorption print PR43.

[0113] Comparative Example 12 Furthermore, the substrate was changed to a 12 μm-thick polyethylene terephthalate film E-5102 (abbreviation: PET, manufactured by Toyobo Co., Ltd.), and the LAMREK medium used in Example 10 was adjusted to a viscosity of 17 seconds using a Zahn cup No. 3 with a dilution solvent (40 parts MEK, 40 parts propyl acetate, 20 parts isopropyl alcohol), and then printed at a film thickness of 1.1 μm to obtain an adsorption print PR44.

[0114] (Comparative Examples 13, 15, 17 and 19) As in Example 18, the adsorption ink G5 was used, and the film thickness was changed to 0.05 μm, as shown in Table 3, to obtain the adsorption print PR45. Similarly, as shown in Table 3, the adsorption ink was changed, and the adsorption prints PR47, PR49, and PR51 were obtained, respectively.

[0115] (Comparative Examples 14, 16, 18 and 20) As in Example 18, the adsorption ink G5 was used, and the film thickness was changed to 6.0 μm, as shown in Table 3, to obtain the adsorption print PR46. Similarly, as shown in Table 3, the adsorption ink was changed, and the adsorption prints PR48, PR50, and PR52 were obtained, respectively.

[0116] The adsorptive prints of Examples 14 to 48 and Comparative Examples 2 to 20 were evaluated for adsorptiveness and blocking resistance, and the results are shown in Tables 2 and 3. If the blocking resistance is poor, ink peeling occurs and the condition of the printed surface deteriorates, making it difficult to use the prints in laminates.

[0117] <Blocking resistance> The printed material was cut into pieces measuring 3cm x 3cm, the printed surface was placed over the non-printed surface, and the material was then subjected to a 500g / cm2 test at 50°C for 24 hours. 2 After applying a load of 1000 mm, the overlapping portion of the printed and non-printed surfaces was peeled off, and the state of ink peeling was observed, and the peeling resistance at that time was evaluated. Those that showed no ink peeling or peeling resistance were judged to have good blocking resistance. Ink peeling and peeling resistance were evaluated on a three-point scale: ○: no ink peeling or peeling resistance, △: slight ink peeling was observed and there was peeling resistance (no practical problems), ×: ink peeling was observed over the entire surface and there was considerable peeling resistance. In the above criteria, for Comparative Example 14 (PR46), Comparative Example 16 (PR48), Comparative Example 18 (PR50), and Comparative Example 20 (PR52) in which the blocking resistance was evaluated as "x", the adsorption of the laminate was not evaluated. In Table 3, this is indicated by "-".

[0118] <Adsorption properties of adsorbent printed matter> A sample piece cut from the adsorption print to a size of 10 cm x 10 cm was placed in a polyvinyl fluoride bag with a rubber stopper and sealed by heat sealing. 3 L of air was then sealed in through the rubber stopper, and test gas (formaldehyde) was added to a gas concentration of 40 ppm, and the bag was left to stand at room temperature. The gas concentration in the bag was measured using a detector tube through the rubber stopper at regular intervals (10 minutes, 1 hour, 3 hours, 6 hours, and 24 hours). When the gas concentration fell below the lower limit of quantification (1 ppm), the measurement was terminated at that point. In addition, a blank test was performed by performing the same operation as above without putting in the sample piece. The measured gas concentration after 24 hours was compared to evaluate the adsorption. The gas concentration after 24 hours was also considered to be the gas concentration after 24 hours, even if the measurement was terminated because the gas concentration fell below the lower limit of quantification before 24 hours. The lower the gas concentration after 24 hours, the better the adsorption was judged to be. The evaluation was based on two levels: Good: Gas concentration after 24 hours was less than 40 ppm; Bad: Gas concentration after 24 hours remained at 40 ppm.

[0119] [Laminated body production] Impact-resistant polystyrene resin E640N (abbreviation: HIPS, manufactured by Toyo Polystyrene Co., Ltd.) was melt-extruded onto the adsorbent ink layer of the adsorbent printed matter PR1 using an extrusion laminator at a line speed of 100 m / min, and laminated at a thickness of 200 μm to obtain a PR1 / / HIPS laminate LAM1.

[0120] Similarly, the adsorption printed matter PR1 was replaced with the adsorption printed matters PR2 to PR4, PR11, PR23, PR24, PR35 and PR42 to obtain laminates LAM2 to LAM4, LAM12, LAM24, LAM25, LAM36 and LAM44.

[0121] Similarly, Takelac A-969V / A-5 (abbreviation: DL, manufactured by Mitsui Chemicals, Inc.) was applied onto the adsorption ink layer of the adsorption printed matter PR5 using 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 then laminated thereon, and the resultant was aged at 40°C for 24 hours to obtain a PR5 / DL / CPP laminate LAM5. Similarly, the adsorption printed matter PR5 was replaced with the adsorption printed matters PR14 to PR18, PR29 to PR34, PR36, PR45, PR47, PR49 and PR51 to obtain laminates LAM15 to LAM19, LAM30 to LAM35, LAM37 and LAM47 to LAM50.

[0122] Similarly, instead of the adsorption printed material PR5, the adsorption printed material PR6 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 then a 60 μm thick unstretched polypropylene film, Torayfan NO ZK93KM (abbreviation: Reto CPP, manufactured by Toray Film Processing Co., Ltd.), was laminated, and then aging was performed at 40°C for 24 hours to obtain a PR6 / DL / Reto CPP laminate LAM6. Similarly, the adsorption printed matter PR6 was replaced with the adsorption printed matter PR37 to obtain a laminate LAM38.

[0123] Similarly, Takelac A-969V / A-5 (abbreviation: DL, manufactured by Mitsui Chemicals, Inc.) was applied onto the adsorption ink layer of the adsorption printed matter PR6 using A-Bar OSP-10 (manufactured by OSG System Products, Inc.), and aging was carried out for 24 hours at 40°C, replacing it with Rix L-4102 (abbreviation: LLDPE, manufactured by Toyobo Co., Ltd.), a 40 μm thick unstretched polyethylene film, to obtain a PR6 / DL / LLDPE laminate LAM7. Similarly, the adsorption printed matter PR6 was replaced with the adsorption printed matter PR37 to obtain a laminate LAM39.

[0124] Similarly, instead of the adsorption printed material PR5, 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 thereon, and then aging was performed at 40°C for 24 hours to obtain a PR7 / DL / LLDPE laminate LAM8. Similarly, the adsorption printed matter PR7 was replaced with the adsorption printed matter PR38 to obtain a laminate LAM40.

[0125] Similarly, the adsorption printed material PR5 was replaced with the adsorption printed material PR8, and Takelac A-525 / Takenate A-52 (manufactured by Mitsui Chemicals, Inc.) was coated with A-Bar OSP-10 (manufactured by OSG System Products, Inc.), and a 60 μm thick unstretched polypropylene film, Torayfan NO ZK93KM (abbreviation: Reto CPP, manufactured by Toray Film Processing Co., Ltd.), was used instead. The resulting laminate was aged at 40°C for 24 hours to obtain a PR8 / DL / Reto CPP laminate LAM9. Similarly, the adsorption printed matter PR8 was replaced with the adsorption printed matter PR39 to obtain a laminate LAM41.

[0126] The PE layer of the substrate of the adsorption printed matter PR9 functions as a heat seal layer, so that the PE layer was used as it is to form the laminate LAM10. Similarly, the adsorption printed materials PR19, PR20, and PR40 were directly used as laminates LAM20, LAM21, and LAM42.

[0127] The opposite side (on the paper) of the adsorption ink layer of the adsorption print PR10 was subjected to a corona treatment, and low-density polyethylene resin Petrothene 204 (abbreviation: LDPE40, manufactured by Tosoh Corporation) was melt-extruded and laminated at 40 μm using an extrusion laminator at a line speed of 100 m / min. Further, the adsorption ink layer was subjected to a corona treatment, and low-density polyethylene resin Petrothene LW01 (abbreviation: LDPE20, manufactured by Tosoh Corporation) was melt-extruded and laminated at 20 μm to obtain a laminate LAM11 of LDPE20 / / PR10 / / LDPE40. (" / / " indicates extrusion lamination.) Similarly, the adsorption printed matter PR10 was replaced with the adsorption printed matters PR21, PR22, and PR41 to obtain laminates LAM22, LAM23, and LAM43.

[0128] Impact-resistant polystyrene resin E640N (abbreviation: HIPS, manufactured by Toyo Polystyrene Co., Ltd.) was melt-extruded onto the adsorbent ink layer of the adsorbent printed matter PR11 using an extrusion laminator at a line speed of 100 m / min, and laminated at a thickness of 200 μm to obtain a PR11 / / HIPS laminate LAM12. Similarly, the adsorption printed matter PR11 was replaced with the adsorption printed matters PR23, PR24 and PR42 to obtain laminates LAM24, LAM26 and LAM44.

[0129] Homopolypropylene resin E111G (abbreviation: PP, MFR = 0.5 g / 10 min, manufactured by Prime Polymer Co., Ltd.) was melt-extruded onto the adsorbent ink layer of the adsorbent printed matter PR12 using an extrusion laminator at a line speed of 100 m / min, and laminated at a thickness of 600 μm to obtain a PR12 / LD / / PP laminate LAM13. Similarly, the adsorption print PR12 was replaced with the adsorption print PR25, PR26, and PR43 to obtain laminates LAM26, LAM27, and LAM45.

[0130] Takelac A-525 / Takenate A-52 (manufactured by Mitsui Chemicals, Inc.) and A-Bar OSP-10 (manufactured by OSG System Products, Inc.) were applied onto the adsorption ink layer of the adsorption printed matter PR13, and a 60 μm-thick unstretched polypropylene film, Torayfan NO ZK93KM (abbreviation: CPP, manufactured by Toray Film Processing Co., Ltd.), was then laminated thereon, and the resulting product was aged at 40° C. for 24 hours to obtain a PR13 / DL / CPP laminate LAM14. Similarly, the adsorption print PR13 was replaced with the adsorption print PR27, PR28, and PR44 to obtain laminates LAM28, LAM29, and LAM46.

[0131] The adsorptivity of the laminates LAM1 to LAM50 was evaluated, and the results are shown in Tables 2 and 3.

[0132] <Adsorption properties of laminate> A sample piece cut from the laminate to a size of 10 cm x 10 cm was placed in a polyvinyl fluoride bag with a rubber stopper and sealed by heat sealing, after which 3 L of air was sealed in through the rubber stopper, and further test gas (formaldehyde) was added so that the gas concentration was 40 ppm, and this was left to stand at room temperature. The gas concentration in the bag was measured using a detector tube through the rubber stopper at regular intervals (10 minutes, 1 hour, 3 hours, 6 hours, 24 hours). When the gas concentration was below the lower limit of quantification (1 ppm), the measurement was terminated at that point. In addition, a blank test was performed by performing the same operation as above without putting in the sample piece. The measured gas concentration after 24 hours was compared to evaluate the adsorption. The gas concentration after 24 hours was also considered to be the gas concentration after 24 hours for those that were below the lower limit of quantification before 24 hours and the measurement was terminated. The lower the gas concentration after 24 hours, the better the adsorption was judged to be. The evaluation was based on two levels: Good: Gas concentration after 24 hours was less than 40 ppm; Bad: Gas concentration after 24 hours remained at 40 ppm.

[0133] [Table 2]

[0134] [Table 3]

[0135] According to Tables 2 and 3, it is clear that the adsorption inks G1 to G13 of Examples 1 to 13 have good adsorption properties based on the results of Examples 14 to 48. It is also clear that the adsorption prints PR1 to PR34 have good blocking resistance. It is clear that the effect of adsorption is not achieved based on the results of Comparative Example 1, which does not use a compound containing at least one of a primary amino group, a secondary amino group, and a tertiary amino group. It is clear that the effect of adsorption is not achieved based on the results of Comparative Examples 2 to 12, which do not use the adsorption ink of the present invention. It is clear that the effect of adsorption is not achieved when the printing film thickness is smaller than the appropriate range (PR45, PR47, PR49, PR51) even when the adsorption ink of the present invention is used. On the other hand, when the printing film thickness is large, blocking resistance is poor, ink peeling occurs, and the state of the printed surface deteriorates. It is clear that although there may be an effect of adsorption, it is difficult to use the printed matter (PR46, PR48, PR50, PR52) in a laminate. Therefore, in addition to being able to suppress the unpleasant odor of aldehyde compounds that is generated when ingredients containing unsaturated fatty acids and amino acids, such as seafood and other meat products, seeds, and grains, are processed or cooked, and aldehydes such as formaldehyde and acetaldehyde that volatilize from materials used in buildings and furniture, etc., it is possible to produce printed materials and laminates that are suitable for printing using a simple process.

Claims

1. A gravure ink composition for adsorbing an aldehyde compound, which is used for an aldehyde compound-adsorbing printed matter having a substrate and an aldehyde compound-adsorbing layer having a thickness of 0.1 to 5 μm on at least one side of the substrate, The gravure ink composition for adsorbing an aldehyde compound comprises at least one kind (A) of an N,N-dialkylaminoalkyl (meth)acrylate compound and a polyethyleneimine compound represented by the following general formula (3), at least one resin (b1) of a urethane resin, a (meth)acrylic resin, a polyamide resin, soluble nitrocellulose, a chlorinated polyolefin resin, and a vinyl chloride-vinyl acetate copolymer resin, and a solvent (C). 【Chemistry 1】 (In formula (3), R 3 and R 4 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or an alkyl group having an alicyclic structure having 6 to 12 carbon atoms; R 5 represents a hydrogen atom, a linear alkyl group having 1 to 18 carbon atoms, or an alkyl group having an alicyclic structure having 6 to 12 carbon atoms; m represents an integer of 2 to 6; and n represents an integer of 20 to 3,000.)

2. The gravure ink composition for adsorbing aldehyde-based compounds comprises at least one (A) of an N,N-dialkylaminoalkyl (meth)acrylate compound and a polyethyleneimine compound represented by the following general formula (3), a thermoplastic resin (B) which is a combination of at least one (b1) of a urethane resin, a (meth)acrylic resin, a polyamide resin, nitrocellulose, a chlorinated polyolefin resin, and a vinyl chloride-vinyl acetate copolymer resin, and another thermoplastic resin (b2), and a solvent (C), when the total content of the gravure ink composition for adsorbing aldehyde-based compounds is taken as 100% by weight: The gravure ink composition for adsorbing aldehyde compounds contains 0.5 to 20% by weight of an N,N-dialkylaminoalkyl (meth)acrylate compound, and at least one of (A) a polyethyleneimine compound represented by the following general formula (3), a thermoplastic resin (B) containing a thermoplastic resin including at least one resin (b1) selected from the group consisting of urethane resin, (meth)acrylic resin, polyamide resin, nitrocellulose, chlorinated polyolefin resin, and vinyl chloride-vinyl acetate copolymer resin, and other thermoplastic resins (b2), the thermoplastic resin (B) being 1 to 30% by weight in terms of solid content; 2. The gravure ink composition for adsorbing aldehyde compounds according to claim 1, further comprising a solvent (C) of 65 to 98% by weight. 【Chemistry 2】 (In formula (3), R 3 and R 4 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or an alkyl group having an alicyclic structure having 6 to 12 carbon atoms; R 5 represents a hydrogen atom, a linear alkyl group having 1 to 18 carbon atoms, or an alkyl group having an alicyclic structure having 6 to 12 carbon atoms; m represents an integer of 2 to 6; and n represents an integer of 20 to 3,000.)

3. 3. An aldehyde-based compound adsorption printed matter, comprising: an aldehyde-based compound adsorption layer formed by laminating the gravure ink composition for adsorbing an aldehyde-based compound according to claim 1 or 2 on at least one surface of a substrate, the ink layer having a thickness of 0.1 to 5 μm.

4. 3. A laminate comprising: an aldehyde compound adsorption layer formed by laminating the gravure ink composition for adsorbing an aldehyde compound according to claim 1 or 2 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 on the aldehyde compound adsorption layer or on the substrate on the opposite surface of the aldehyde compound adsorption layer.

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 or 5, 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 aldehyde compounds according to claim 1 or 2 on at least one of the substrates to form an aldehyde compound adsorption layer having an ink layer thickness of 0.1 to 5 μm.

8. Providing a substrate; a gravure printing step of forming an aldehyde compound adsorption layer by printing the gravure ink composition for adsorbing an aldehyde compound according to claim 1 or 2 on at least one of the substrates in a 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 aldehyde compound adsorption layer or on the substrate on the opposite side of the aldehyde compound adsorption layer; A method for producing a laminate, comprising:

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. The method for producing a laminate according to claim 8 or 9, characterized in that the lamination process is a lamination process for forming at least one laminate layer among a dry lamination process, a non-solvent lamination process, a thermal lamination process, an extrusion lamination process, a co-extrusion lamination process, and a PE sandwich lamination process.

11. A packaging bag essentially comprising a substrate, an aldehyde compound-adsorption layer laminated to a thickness of 0.1 to 5 μm, and a sealant layer or a sealing layer, wherein the aldehyde compound-adsorption layer is formed from the gravure ink composition for adsorbing aldehyde compounds according to claim 1 or 2.

12. A packaging container essentially comprising a substrate, an aldehyde compound-adsorption layer laminated to a thickness of 0.1 to 5 μm, and an extrusion laminate layer, wherein the aldehyde compound-adsorption layer is formed from the gravure ink composition for adsorbing aldehyde compounds according to claim 1 or 2.

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