Sulfur compound adsorbent laminate, method for producing sulfur compound adsorbent laminate, and packaging bag

Abstract

The present invention provides a laminate and packaging bag that, even with a sulfur compound adsorption layer having a specific area, can suppress unpleasant sulfur compound odors generated when contents containing sulfur compounds, such as seafood, meat products, egg products, and rice products, are heat-treated, and can also suppress unpleasant sulfur compound odors generated from contents containing sulfur compounds that are not heat-treated, such as rice crackers. Furthermore, even when the sulfur compound adsorption layer of a specific area is overprinted with a gravure printing ink layer, the laminate and packaging bag have good blocking resistance and reduced residual solvents. [Solution] A sulfur-based compound adsorption laminate comprising a sulfur-based compound adsorption layer with a thickness of 0.5 to 5 μm formed by coating using a multi-color gravure printing method, a gravure printing ink layer with a thickness of 0.01 to 10 μm formed by coating using a multi-color gravure printing method, and a laminate layer, wherein the sulfur-based compound adsorption layer covers 10% to 99% of the total surface area forming the adsorption layer, and the sulfur-based compound adsorption layer is composed of zinc oxide, urethane resin, and (meth)acrylic A sulfur-based compound adsorbent laminate comprising a layer made of a gravure ink composition for adsorbing sulfur-based compounds, which includes at least one resin from among resins, polyamide resins, nitrated cotton, chlorinated polyolefin resins, and vinyl chloride / vinyl acetate copolymer resins, and an organic solvent, characterized in that when the sulfur-based compound adsorbent laminate cut to 10 cm x 10 cm and hydrogen sulfide in 3 L of air so that the gas concentration is 20 ppm are placed in a bag, sealed, and left to stand at room temperature for 24 hours, the hydrogen sulfide gas concentration is less than 20 ppm.

Description

[Technical Field]

[0001] The present invention relates to a laminate that suppresses unpleasant odor caused by sulfur compounds generated from contents containing sulfur compounds, such as meat products including fish and shellfish, egg products, cooked rice, and rice crackers. [Background Art]

[0002] Sulfur-containing amino acids (such as cystine, methionine, cysteine, and α-lipoic acid) among the amino acids constituting proteins contained in meat products including fish and shellfish, egg products, cooked rice, and rice crackers generate unpleasant odor when these products are boiled, retorted, cooked (fried), or over time. This odor derives from sulfur-based compounds generated via hydrolysis of the sulfur-containing amino acids among the amino acids constituting said proteins, including hydrogen sulfide, methyl sulfide, methyl disulfide, methyl trisulfide, methyl mercaptan, ethyl mercaptan, t-butyl mercaptan, n-propyl mercaptan, and isopropyl mercaptan. Since these odors affect the taste and flavor of food, various studies have been conducted to suppress them.

[0003] To suppress such odors, methods including kneading deodorant components into a film and enclosing a deodorant desiccant together with the food have been proposed, but these methods have many problems such as risk of accidental ingestion, increased cost, and inability to enclose the desiccant with certain types of food.

[0004] Patent Document 1 proposes a sulfur-based compound adsorption print that forms a sulfur-based compound adsorption layer on at least one surface of a substrate with an ink layer thickness of 0.1 to 5 μm, comprising a gravure ink composition for adsorbing sulfur-based compounds characterized by comprising zinc oxide (A), at least one resin (b1) from among urethane resin, (meth)acrylic resin, polyamide resin, nitrated cotton, chlorinated polyolefin resin, and vinyl chloride / vinyl acetate copolymer resin, and a solvent (C). This composition suppresses the unpleasant sulfur compound odor generated when the contents are heat-treated. It also states that the sulfur-based compound adsorption layer may include other ink layers formed by laminating other gravure ink compositions, and that since it is formed by coating using a gravure printing method, not only full-color printing but also partial printing is possible. However, the examples only disclose those using a solid plate (i.e., full-color printing), and there is no disclosure of lamination with other gravure ink compositions. Therefore, further investigation is needed to solve the same problem with such laminates. Furthermore, residual solvents in the printed material may cause odors and may impair printability (blocking resistance). In addition, Patent Document 1 lists rice crackers as a heat-treated product, and it is understood that there is an effect in suppressing the unpleasant sulfur compound odor generated during heat treatment. However, the packaging bags containing rice crackers are displayed and sold in stores as is (i.e., they are not heat-treated). However, even with products like rice crackers that are not heat-treated, an unpleasant sulfur compound odor may develop over time, and consumers may perceive this as an unpleasant odor when they open the package. However, Patent Document 1 does not evaluate actual packaging that is not heat-treated, and further investigation is needed regarding the effect of forming surface area in suppressing sulfur compound odors. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2022-099681 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] Therefore, the present invention aims to provide a laminate and packaging bag that, even with a sulfur compound adsorption layer having a specific area range, can suppress unpleasant sulfur compound odors generated when contents containing sulfur compounds, such as seafood, meat products, egg products, and rice products, are heat-treated, and can also suppress unpleasant sulfur compound odors generated from contents containing sulfur compounds that are not heat-treated, such as rice crackers, and that also exhibits good blocking resistance and reduced residual solvents even when a sulfur compound adsorption layer of a specific area range and a gravure printing ink layer are overprinted. [Means for solving the problem]

[0007] The present inventors have developed a sulfur-based compound adsorption laminate comprising a sulfur-based compound adsorption layer with a thickness of 0.5 to 5 μm formed by coating using a multi-color gravure printing method, a gravure printing ink layer with a thickness of 0.01 to 10 μm formed by coating using a multi-color gravure printing method, and a laminate layer, wherein the sulfur-based compound adsorption layer covers 10% to 99% of the total surface area forming the adsorption layer, and the sulfur-based compound adsorption layer is composed of zinc oxide, urethane resin, (meth)acrylic resin, polyamide resin, nitrated cotton, salt The present invention was completed by discovering that the above problem can be solved by a sulfur-based compound adsorption laminate, which is a layer made of a gravure ink composition for adsorbing sulfur-based compounds containing at least one resin from polyolefin resin and vinyl chloride / vinyl acetate copolymer resin and an organic solvent, and is characterized in that when the sulfur-based compound adsorption laminate cut to 10 cm x 10 cm and hydrogen sulfide in 3 L of air so that the gas concentration is 20 ppm are placed in a bag, sealed, and left to stand at room temperature for 24 hours, the hydrogen sulfide gas concentration is less than 20 ppm.

[0008] In other words, the present invention is (1) A sulfur-based compound adsorbent laminate comprising a sulfur-based compound adsorbent layer with a thickness of 0.5 to 5 μm formed by coating using a multi-color gravure printing method, a gravure printing ink layer with a thickness of 0.01 to 10 μm formed by coating using a multi-color gravure printing method, and a laminate layer, The sulfur-based compound adsorption layer has an area of ​​10% or more and 99% or less when the total surface area of ​​the surface forming the adsorption layer is taken as 100%. The sulfur-based compound adsorption layer is a layer made of a gravure ink composition for adsorbing sulfur-based compounds, comprising zinc oxide, at least one resin from among urethane resin, (meth)acrylic resin, polyamide resin, nitrated cotton, chlorinated polyolefin resin, and vinyl chloride / vinyl acetate copolymer resin, and an organic solvent. A sulfur-based compound adsorbent laminate, characterized in that when a 10cm x 10cm piece of the sulfur-based compound adsorbent laminate and hydrogen sulfide are placed in a bag with a gas concentration of 20 ppm in 3L of air, sealed, and left standing at room temperature for 24 hours, the hydrogen sulfide gas concentration is less than 20 ppm. (2) The sulfur compound adsorbent laminate according to (1), characterized in that the laminate layer is a sealant layer or a sealing layer. (3) The sulfur compound adsorbent laminate according to (1) or (2), characterized in that the laminate layer is at least one laminate layer selected from dry laminate, non-solvent laminate, heat laminate, extruded laminate, co-extruded laminate, and PE sandwich laminate. (4) A method for producing a sulfur-based compound adsorbent laminate, comprising a multicolor gravure printing step by a multicolor gravure printing method to produce a sulfur-based compound adsorbent layer, which is made by printing a sulfur-based compound adsorbent layer to a film thickness of 0.5 to 5 μm using a gravure ink composition for adsorbing sulfur-based compounds, which comprises zinc oxide, at least one resin selected from urethane resin, (meth)acrylic resin, polyamide resin, nitrated cotton, chlorinated polyolefin resin, and vinyl chloride / vinyl acetate copolymer resin, and an organic solvent, and a gravure printing ink layer, which is made by printing a gravure printing ink to a film thickness of 0.01 to 10 μm, and a lamination step, The sulfur-based compound adsorption layer has an area of ​​10% or more and 99% or less when the total surface area of ​​the surface forming the adsorption layer is taken as 100%. A method for producing a sulfur-based compound adsorbent laminate, characterized in that when the sulfur-based compound adsorbent laminate cut to 10 cm x 10 cm by the above production method and hydrogen sulfide are placed in a bag so that the gas concentration in 3 L of air is 20 ppm, the bag is sealed, and the bag is left standing at room temperature for 24 hours, the hydrogen sulfide gas concentration is less than 20 ppm. (5) A method for producing a sulfur-based compound adsorbent laminate according to (4), characterized in that the laminating step is a laminating step for forming a sealant layer or a coating step for forming a seal layer. (6) A method for producing a sulfur-based compound adsorbent laminate according to (4) or (5), characterized in that the lamination step is a lamination step that forms at least one laminate layer from among a dry lamination step, a non-solvent lamination step, a heat lamination step, an extrusion lamination step, a co-extrusion lamination step, and a PE sandwich lamination step. (7) A packaging bag that requires a sulfur-based compound adsorption layer with a thickness of 0.5 to 5 μm, a gravure printing ink layer with a thickness of 0.01 to 10 μm, and a sealant layer or sealing layer, The sulfur-based compound adsorption layer has an area of ​​10% or more and 99% or less when the total surface area of ​​the surface forming the adsorption layer is taken as 100%. The sulfur-based compound adsorption layer is a layer made of a gravure ink composition for adsorbing sulfur-based compounds, characterized by containing zinc oxide, at least one resin from among urethane resin, (meth)acrylic resin, polyamide resin, nitrated cotton, chlorinated polyolefin resin, and vinyl chloride / vinyl acetate copolymer resin, and an organic solvent. A packaging bag characterized in that, when contents containing a sulfur compound are placed in the aforementioned packaging bag, the opening is heat-sealed at 190°C for 1 second, and then left to stand at 50°C for 24 hours, there is no sulfurous odor. (8) A packaging bag that requires a sulfur-based compound adsorption layer with a thickness of 0.5 to 5 μm, a gravure printing ink layer with a thickness of 0.01 to 10 μm, and a sealant layer or sealing layer, The sulfur-based compound adsorption layer has an area of ​​10% or more and 99% or less when the total surface area of ​​the surface forming the adsorption layer is taken as 100%. The sulfur-based compound adsorption layer is a layer made of a gravure ink composition for adsorbing sulfur-based compounds, characterized by containing zinc oxide, at least one resin from among urethane resin, (meth)acrylic resin, polyamide resin, nitrated cotton, chlorinated polyolefin resin, and vinyl chloride / vinyl acetate copolymer resin, and an organic solvent. A packaging bag characterized in that, when contents containing a sulfur compound are placed in the aforementioned packaging bag, the opening is sealed by heat sealing at 190°C for 1 second, and then left to stand at 25°C for 48 hours, there is no sulfurous odor. This concerns... [Effects of the Invention]

[0009] According to the present invention, even if the sulfur compound adsorption layer has a specific area range, it is possible to suppress unpleasant sulfur compound odors that occur when contents containing sulfur compounds, such as seafood, meat products, egg products, and rice products, are heat-treated, and to suppress unpleasant sulfur compound odors that occur from contents containing sulfur compounds that are not heat-treated, such as rice crackers. In addition, even when a sulfur compound adsorption layer with a specific area range is overprinted with a gravure printing ink layer on the adsorption layer, a laminate and packaging bag can be provided that have good blocking resistance and reduced residual solvent. [Modes for carrying out the invention]

[0010] The embodiments for carrying out the present invention will be described in detail below. It should be noted that this embodiment is merely one embodiment for carrying out the present invention, and the present invention is not limited to this embodiment. Various modifications and embodiments are possible without departing from the spirit of the present invention.

[0011] In the following explanation, (meth)acrylic and (meth)acrylate refer to acrylic and methacrylic, and acrylate and methacrylate, respectively.

[0012] The sulfur-based compound adsorbing laminate of the present invention (hereinafter, also simply referred to as "adsorbing laminate") is a sulfur-based compound adsorbing laminate obtained by laminating a sulfur-based compound adsorbing layer having a film thickness of 0.5 to 5 µm formed by coating through a multi-color gravure printing method, a gravure printing ink layer having a film thickness of 0.01 to 10 µm formed by coating through a multi-color gravure printing method, and a laminate layer, wherein when the total area of the surface on which the sulfur-based compound adsorbing layer is formed is defined as 100%, the area of the sulfur-based compound adsorbing layer is 10% or more and 99% or less, the sulfur-based compound adsorbing layer is a layer formed of a gravure ink composition for sulfur-based compound adsorption containing zinc oxide, at least one resin selected from the group consisting of urethane resins, (meth)acrylic resins, polyamide resins, nitrocellulose, chlorinated polyolefin resins and vinyl chloride-vinyl acetate copolymer resins, and an organic solvent, and it is preferable that when the sulfur-based compound adsorbing laminate cut into a size of 10 cm × 10 cm and hydrogen sulfide adjusted to a gas concentration of 20 ppm in 3 L of air are placed in a bag, sealed, and then allowed to stand at room temperature for 24 hours, the hydrogen sulfide gas concentration is less than 20 ppm.

[0013] The sulfur-based compound adsorbing laminate of the present invention preferably comprises a sulfur-based compound adsorbing layer having a film thickness of 0.5 to 5 µm formed by coating through a multi-color gravure printing method, and the film thickness is more preferably 0.3 to 3 µm. If the thickness is less than 0.5 µm, the adsorptivity for sulfur-based compounds decreases. If the thickness is more than 5 µm, the blocking resistance is poor.

[0014] In the sulfur-based compound adsorbing laminate of the present invention, it is preferable to laminate a gravure printing ink layer having a film thickness of 0.01 to 10 µm formed by coating through a multi-color gravure printing method. The film thickness of the gravure printing ink layer is preferably 0.01 to 10 µm, more preferably 0.1 to 5 µm, and still more preferably 1 to 3 µm. If the thickness is less than 0.01 µm, it is difficult to obtain sufficient density, and if the thickness is more than 10 µm, it is difficult to provide the gravure printing ink layer and the blocking resistance is poor.

[0015] In the sulfur-based compound adsorbing laminate of the present invention having a configuration in which the sulfur-based compound adsorbing layer and a gravure printing ink layer are laminated, when the total area of the surface on which the sulfur-based compound adsorbing layer is formed is defined as 100%, the sulfur-based compound adsorbing layer is preferably formed in an area of 10% or more and 99% or less, more preferably formed in an area of 20% or more and 80% or less, and still more preferably formed in an area of 30% or more and 60% or less. When the formation area of the sulfur-based compound adsorbing layer falls within the above range, even when overprinting is performed with the gravure printing ink layer, good blocking resistance can be obtained, the residual solvent can be reduced, and the odor from the printed matter is also reduced.

[0016] The sulfur-based compound adsorbing laminate of the present invention is preferably laminated with a laminate layer. As for the adsorbing laminate, the higher the lamination strength is, the better the lamination property can be determined to be. If the lamination strength is 80 g or more, the laminate is sufficiently applicable, eliminating the risk of insufficient sealing strength during bag making, and reduces bag breakage caused by dropping during distribution when the product is filled into a packaging bag, and reduces the difficulty of opening for consumers when opening the package.

[0017] The lamination strength referred to in the present invention is obtained by cutting the adsorbing laminate into a 15-mm-wide strip to prepare a test piece, preparing five such test pieces, performing T-peeling at the substrate / sulfur-based compound adsorption interface using a universal tensile tester (RTE-1210, manufactured by Orientec Co., Ltd.) at a tensile speed of 300 mm / min, measuring the lamination strength of each test piece five times, and calculating the average value thereof.

[0018] The laminate layer is preferably a sealant layer or a sealing layer. Examples of the sealant layer include a layer formed by laminating a heat-sealable laminate, bonding a known sealant film, or performing resin coating by an extrusion lamination method, and examples of the sealing layer include a layer formed by coating a heat sealant or a hot melt adhesive.

[0019] As long as sufficient sealing strength can be ensured, the bonding method for the sealant layer can be appropriately selected according to the substrate, application, and composition. For example, bonding a known sealant film to a sulfur-based compound adsorption layer on the substrate via an adhesive (dry lamination method, non-solvent lamination method, wet lamination method), bonding by heat (thermal lamination method), and resin coating by extrusion lamination method (extrusion lamination method, co-extrusion lamination method, PE sandwich lamination method) can be preferably used. Laminates can be manufactured by using one or a combination of these methods. There are no particular restrictions on the thickness of the sealant layer, but it is preferable that the thickness be 2 to 200 μm for sealant films and 1 to 100 μm for resin coatings applied by the extrusion lamination method.

[0020] 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. The film may be stretched or unstretched, and one or more types may be laminated.

[0021] When using adhesives in the dry lamination method, non-solvent lamination method, wet lamination method, extrusion lamination method, etc., commercially available adhesives are acceptable. Examples include two-component or one-component urethane resin adhesives, acrylic, epoxy, polyester, polyethyleneimine, polybutadiene, water-based urethane, isocyanate, organotitanium, starch-based water-soluble adhesives, and water-based adhesives such as vinyl acetate emulsion. Known application methods can be used for applying the adhesive to form the sealant layer. For example, roll coaters, reverse roll coaters, gravure offset coaters, gravure coaters, microgravure coaters, knife coaters, bar coaters, wire bar coaters, die coaters, and dip coaters can be used. There are no particular restrictions on the thickness of the adhesive, but a range of approximately 0.001 to 10 μm is preferred, and a range of 0.01 to 5 μm is particularly preferred.

[0022] Examples of resins that can be used for resin coating by the extrusion lamination method include polyethylene resins such as LDPE, LLDPE, and HDPE; polypropylene resins; 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 or fumaric acid; polystyrene resins; and thermoplastic resins such as polybutylene terephthalate resins. One or more of these resins may be used.

[0023] The sealing layer can be formed using a method that ensures sufficient sealing strength, and the method of formation can be appropriately selected depending on the substrate, application, and structure. For example, coating with a heat sealant or hot melt adhesive is preferably used. These methods can be used individually or in combination to produce the laminate. There are no particular restrictions on the thickness of the sealing layer, but it is preferably 1 to 50 μm for hot melt adhesive coating and 0.01 to 30 μm for heat sealant coating. Adhesives or other adhesives may also be used.

[0024] Examples of the resins used in the heat-sealing agent include thermoplastic resins such as vinylidene chloride, shellacs, rosins, rosin-modified maleic acid resins, rosin-modified phenolic resins, nitrated cotton, cellulose acetate, cellulose acetylpropionate, cellulose acetyl butyrate, chlorinated rubber, cycloadhesive 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. These can be used individually or in combination of two or more types. These resins can be dissolved in a solvent, or dispersed in water as acrylic emulsions, urethane emulsions, ethylene-vinyl alcohol emulsions, polyethylene emulsions, polypropylene emulsions, or ethylene vinyl acetate emulsions.

[0025] Furthermore, it is preferable that the laminate layer is at least one of the following laminate layers: dry lamination, non-solvent lamination, heat lamination, extrusion lamination, co-extrusion lamination, and PE sandwich lamination. The laminate layer can be manufactured by at least one of the following lamination methods: dry lamination, non-solvent lamination, heat lamination, and resin coating by extrusion lamination (extrusion lamination, co-extrusion lamination, and PE sandwich lamination).

[0026] Examples of 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 or fumaric acid; polystyrene resins (general-purpose polystyrene (GPPS), high-impact polystyrene (HIPS), expanded polystyrene (PSP), heat-resistant PSP, etc.); and thermoplastic resins such as polybutylene terephthalate resin. One or more of these resins may be used.

[0027] The sulfur-based compound adsorbent laminate of the present invention is preferably cut into 10 cm x 10 cm pieces so as to cover a predetermined area range of the adsorption layer, placed in a bag with hydrogen sulfide in 3 L of air so that the gas concentration is 20 ppm, sealed, and left standing at room temperature for 24 hours. In this case, the hydrogen sulfide gas concentration is preferably less than 20 ppm, more preferably less than 10 ppm, and even more preferably less than 5 ppm.

[0028] The sulfur-based compound adsorption laminate of the present invention preferably has a sulfur-based compound adsorption layer made of a gravure ink composition for adsorbing sulfur-based compounds (hereinafter also simply referred to as "adsorption ink composition") which comprises zinc oxide, at least one resin selected from urethane resin, (meth)acrylic resin, polyamide resin, nitrated cotton, chlorinated polyolefin resin, and vinyl chloride / vinyl acetate copolymer resin, and an organic solvent.

[0029] The aforementioned zinc oxide has low toxicity, is readily available, and reacts with sulfur compounds such as hydrogen sulfide, which cause odors, to produce zinc sulfide. The resulting zinc sulfide is white and has little effect on the appearance of transparent substrates, making it useful.

[0030] The zinc oxide is preferably in granular form, with an average particle size of 0.01 to 10 μm, and more preferably 0.02 to 5 μm. An average particle size of 0.01 to 10 μm maintains the adsorption effect of sulfur compounds and prevents the zinc oxide from settling over time. If the average particle size is smaller than 0.01 μm, the dispersibility is poor, and if the average particle size is larger than 10 μm, the transparency is poor. The average particle size referred to here is the D50 particle size measured by laser diffraction / scattering. Examples include the laser diffraction / scattering particle size distribution analyzer LA-920 (manufactured by Horiba, Ltd.) and the MICROTRAC 9320-X100 (manufactured by Honeywell).

[0031] The zinc oxide content in the adsorbent ink composition is preferably 1 to 70% by weight, and more preferably 5 to 50% by weight. If the zinc oxide content is less than 1% by weight, the adsorption of sulfur-based compounds is poor, and if the zinc oxide content is more than 70% by weight, the fluidity is poor.

[0032] The adsorbent ink composition of the present invention preferably contains at least one resin from among urethane resin, (meth)acrylic resin, polyamide resin, nitrated cotton, chlorinated polyolefin resin, and vinyl chloride / vinyl acetate copolymer resin. The resins can be prepared by conventional methods. These resins may be one type or two or more types. Commercially available options 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-based) (all manufactured by Tokyo Ink Co., Ltd.).

[0033] The adsorbent ink composition of the present invention may also contain other thermoplastic resins in addition to the urethane resin, (meth)acrylic resin, polyamide resin, nitrated cotton, chlorinated polyolefin resin, and vinyl chloride / vinyl acetate copolymer resin. For example, shellacs, rosins, rosin-modified maleic acid resins, rosin-modified phenolic resins, cellulose acetate, cellulose acetylpropionate, cellulose acetyl butyrate, chlorinated rubber, cyclized rubber, polyethylene resins, polypropylene 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, 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, polyphenylene sulfone resins, polyimide resins, polyamideimide resins, amorphous polyarylate resins, polyetheretherketone resins, polyvinyl alcohol resins, ethylene-vinyl alcohol resins, and polylactic acid are preferred. These resins may be of one type or more than one type. Commercially available options include TPH medium, VESTA medium, LRC-NT medium, and KCNT medium (all manufactured by Tokyo Ink Co., Ltd.).

[0034] In the adsorbent ink composition of the present invention, the content of thermoplastic resins, which are a combination of urethane resin, (meth)acrylic resin, polyamide resin, nitrated cotton, chlorinated polyolefin resin, vinyl chloride / vinyl acetate copolymer resin, and other thermoplastic resins, is preferably 1 to 30% by weight, and more preferably 3 to 20% by weight, on a solid content basis. If the thermoplastic resin content is less than 1% by weight, the film-forming properties of the adsorbent ink composition are poor, and if the thermoplastic resin content is more than 30% by weight, the fluidity of the adsorbent ink composition is poor, resulting in poor manufacturability.

[0035] The adsorbent ink composition of the present invention can use organic solvents commonly used in gravure inks. Examples of such organic solvents include aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane; alcoholic solvents such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, 1-butanol, 2-butanol, isobutanol, and tert-butanol; esteric 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 monoethyl ether. Examples of glycol ether solvents include ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether, as well as their esterified products. As esterified products, acetate-forms are mainly selected, 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, toluene, ethyl acetate, n-propyl acetate, isopropyl alcohol, propylene glycol monomethyl ether, and methyl ethyl ketone are more preferred from the viewpoint of printability and versatility. These can be used individually or in combination of two types. The organic solvent content in the adsorbent ink composition is preferably in 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 suitability for ink manufacturing will be inferior. If it exceeds 98% by weight, the ink film thickness will become locally uneven, resulting in irregular variations in density (swimming phenomenon) on the printed surface, and the viscosity will be low, which may cause zinc oxide to settle easily.

[0036] The adsorbent ink composition may also contain colorants, inorganic fillers, organic fillers, defoamers, leveling agents, antiblocking agents, waxes, pigment dispersants, antistatic agents, slip agents, plasticizers, tackifiers, and the like. Any known and commonly used substances can be appropriately selected as long as they do not impair the properties of the adsorbent ink composition.

[0037] The aforementioned coloring material may contain a pigment, a dye, or a mixture thereof. Examples of pigments include inorganic pigments such as titanium dioxide, iron oxide, barium sulfate, calcium carbonate, silica, zinc oxide, zinc sulfide, mica, talc, and pearl; 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 individually or in combination of two or more types. Dyes are preferably those that dissolve or disperse in a solvent, and may be used individually or in combination of two or more types. Among these, pigments are preferred from the viewpoint of durability.

[0038] The gravure printing ink layer is preferably a layer coated with gravure printing ink containing a resin commonly used in gravure inks (hereinafter also simply referred to as "gravure ink"). Examples of the resin include polyurethane resins, polyolefin resins, shellacs, rosin-modified maleic acid resins, rosin-modified phenolic resins, cellulose acetate, cellulose acetyl propionate, cellulose acetyl butyrate, chlorinated rubber, cyclized rubber, halogenated vinyl resins (e.g., vinyl chloride resins, fluorine-containing vinyl resins, etc.), polyvinyl acetate, vinyl chloride-vinyl acetate copolymers, polystyrene resins, acrylic resins, acrylic styrene copolymers, polyacrylic acid esters, polyester resins, polyvinylidene chloride resins, ketone resins, polyamide resins, nitrocellulose resins, rosin resins, styrene maleic acid resins, alkyd resins, and ethylene-vinyl alcohol resins.

[0039] The resin is preferably present in the gravure ink in a solid content of 1 to 70% by mass, more preferably 2 to 65% by mass, and even more preferably 3 to 60% by mass. If the content is less than 1% by mass, sufficient adhesion cannot be obtained, and if it is more than 70% by mass, the solid content is too high, the viscosity becomes high, and application becomes difficult.

[0040] In addition to resin, the gravure ink may also contain colorants, solvents, inorganic fillers, organic fillers, defoamers, leveling agents, antiblocking agents, waxes, pigment dispersants, antistatic agents, slip agents, plasticizers, tackifiers, antioxidants, surfactants, UV absorbers, surface modifiers, pH adjusters, charge imparters, bactericides, deodorants, wetting agents, anti-skinning agents, metal chelating agents, and the like.

[0041] The aforementioned colorant may contain pigments, dyes, or mixtures thereof. Examples of pigments include inorganic pigments such as titanium dioxide, iron oxide, barium sulfate, calcium carbonate, silica, zinc oxide, zinc sulfide, mica, talc, pearl, aluminum, and carbon black; organic pigments such as phthalocyanine-based, insoluble azo-based, condensed azo-based, dioxazine-based, anthraquinone-based, quinacridone-based, perylene-based, perinone-based, and thioindigo-based pigments; and various other fluorescent pigments, metal powder pigments, and extender pigments. These pigments may be used individually or in combination of two or more types. Dyes are preferably those that dissolve or disperse in a solvent, and may be used individually or in combination of two or more types. Among these, pigments are preferred from the viewpoint of durability. Because it contains a colorant, it is very useful in terms of providing color variations and multi-color images.

[0042] The solvent is used to provide appropriate fluidity and adjust viscosity during the formation of the gravure printing ink layer, and it is preferable that the resin is dissolved or dispersed in the solvent.

[0043] Examples of the aforementioned solvents include aromatic hydrocarbon solvents such as water, toluene, and xylene; aliphatic hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane; alcoholic solvents such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, 1-butanol, 2-butanol, isobutanol, and tert-butanol; esteric 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 monoethyl ether. Examples 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 their esterified products. As esterified products, acetate-forms are mainly selected, 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. These can be used individually or in combination of two types.

[0044] The solvent is preferably present in the gravure ink at a concentration of 1 to 90% by mass, more preferably 5 to 80% by mass, and even more preferably 10 to 70% by mass. If the concentration is less than 1% by mass, sufficient printability cannot be obtained, and if it is more than 90% by mass, the solid content will decrease, reducing the adhesion between the substrate and the sulfur-based compound adsorbent layer.

[0045] Examples of commercially available gravure inks include the LG-FK series (urethane resin) and the NOPL-T series (olefin-based) (both manufactured by Tokyo Ink Co., Ltd.).

[0046] The sulfur-based compound adsorbent laminate of the present invention preferably includes a base material. The base material 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 a barrier layer in the middle; polycarbonate films; polyacrylonitrile films; polyimide films; cellophane; moisture-proof cellophane; transparent vapor-deposited polyester films or transparent vapor-deposited polyamide films having a vapor-deposited layer of alumina or silica on a PET film or polyamide film; various coated films coated with polyvinylidene chloride resin, polyvinyl alcohol resin, polyacrylic acid resin, etc.; 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 considering mechanical strength, dimensional stability, etc. Furthermore, to improve the adhesion of the anchor coat layer and laminate layer to the printed surface, corona treatment, low-temperature plasma treatment, flame treatment, solvent treatment, coating treatment, etc. can be applied, or pre-treated surfaces can be selected. Among these, PET film, polyethylene film, polypropylene film, polyamide film, coated film, transparent vapor-deposited polyester film or transparent vapor-deposited polyamide film, and co-extruded film are preferred. The thickness of the substrate is not particularly limited as long as it does not impair printability and winding suitability, but 5 to 300 μm is preferred, and 6 to 250 μm is more preferred. In addition, if the substrate is a heat-sealable film such as polyethylene film, the substrate itself may function as a sealant layer.

[0047] The paper substrate preferably includes at least one selected from coated paper, uncoated paper, and paper substrates obtained by laminating them with a plastic film, etc. The paper substrate may be laminated by methods such as dry lamination, non-solvent lamination, or extrusion lamination of thermoplastic resins, or by lamination via adhesives, or by combining these methods as appropriate. Laminates with heat-sealing properties can also be used as paper substrates. Methods for imparting heat-sealing properties include lamination of known sealant films, resin coating by extrusion lamination, application of heat-sealing agents or hot melts, or heat-sealing resin processing by co-extrusion. A layer to which heat-sealing properties have been imparted 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 impede printability, winding suitability, etc., but is preferably 5 to 800 μm, and more preferably 6 to 600 μm.

[0048] The sulfur-based compound adsorbent laminate of the present invention has a configuration such as: substrate / gravure printing ink layer / sulfur-based compound adsorbent layer / laminate layer; substrate / sulfur-based compound adsorbent layer / gravure printing ink layer / laminate layer; laminate layer (polyethylene sealant) / sulfur-based compound adsorbent layer / gravure printing ink layer; or laminate layer (polyethylene sealant) / gravure printing ink layer / sulfur-based compound adsorbent layer. Furthermore, an intermediate layer may be laminated to impart or enhance properties such as rigidity, stiffness, gas barrier properties, fragrance retention, moisture resistance, pinhole resistance, dead hole resistance, light shielding properties, and straight cut properties. If an intermediate layer is provided, there are no restrictions on its position. However, it is preferable that the gas barrier layer for imparting gas barrier properties is not provided on the side of the sulfur-based compound adsorbent layer that is closer to the source of the adsorbed substance.

[0049] 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 in the middle; polycarbonate films; polyacrylonitrile films; polyimide films; cellophane; moisture-proof cellophane; transparent vapor-deposited polyester films or transparent vapor-deposited polyamide films with a vapor-deposited layer of alumina or silica on PET film or polyamide film; various coated films coated with polyvinylidene chloride resin, polyvinyl alcohol resin, polyacrylic acid resin, etc.; 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. Appropriate materials can be selected considering mechanical strength and dimensional stability. To improve adhesion, the bonding surfaces can be treated with corona treatment, low-temperature plasma treatment, flame treatment, solvent treatment, coating, or pre-treated surfaces. Treatment of both sides is preferred. The intermediate layer can be any thickness that does not impair printability, winding suitability, etc., with a thickness of 5 to 300 μm being preferred, and a thickness of 6 to 250 μm being more preferred.

[0050] The sulfur-based compound adsorbent laminate of the present invention is preferably used for packaging, food preservation, retort applications, microwave oven applications, agricultural applications, civil engineering applications, fisheries applications, automotive interior and exterior applications, marine applications, daily necessities applications, building material interior and exterior applications, housing equipment applications, medical and medical device applications, pharmaceutical applications, home appliance applications, furniture applications, stationery and office supplies applications, sales promotion applications, commercial applications, electrical and electronic industry applications, and industrial material applications. Among these, it is more preferably used for packaging applications.

[0051] The present invention provides a method for producing a sulfur-based compound adsorbent laminate using a multicolor gravure printing method, which involves printing a sulfur-based compound adsorbent layer to a thickness of 0.5 to 5 μm using a gravure ink composition for sulfur-based compound adsorption containing zinc oxide, at least one resin selected from urethane resin, (meth)acrylic resin, polyamide resin, nitrated cotton, chlorinated polyolefin resin, and vinyl chloride / vinyl acetate copolymer resin, and an organic solvent, and then printing a gravure printing ink layer to a thickness of 0.01 to 10 μm using a multicolor gravure printing method. In a method for manufacturing a sulfur-based compound adsorbent laminate, which includes a gravure printing process and a lamination process, the sulfur-based compound adsorption layer covers an area of ​​10% to 99% of the total surface area forming the adsorption layer, and it is preferable that the hydrogen sulfide gas concentration is less than 20 ppm when the sulfur-based compound adsorption laminate produced by the manufacturing method, cut to 10 cm x 10 cm, and hydrogen sulfide in 3 L of air to a gas concentration of 20 ppm are placed in a bag, sealed, and left to stand at room temperature for 24 hours.

[0052] The present invention's method for producing a sulfur-based compound adsorbent laminate preferably includes a multicolor gravure printing step to create a sulfur-based compound adsorbent layer by printing a gravure ink composition for adsorbing sulfur-based compounds, which comprises zinc oxide, at least one resin selected from urethane resin, (meth)acrylic resin, polyamide resin, nitrated cotton, chlorinated polyolefin resin, and vinyl chloride / vinyl acetate copolymer resin, and an organic solvent, to a film thickness of 0.5 to 5 μm, and more preferably 0.3 to 3 μm. If the film thickness is less than 0.5 μm, the adsorption capacity of sulfur-based compounds decreases. If the film thickness is greater than 5 μm, the blocking resistance is poor.

[0053] The method for producing the sulfur-based compound adsorbent laminate of the present invention preferably further includes a multi-color gravure printing step by a multi-color gravure printing method to create a gravure printing ink layer by printing gravure printing ink to a film thickness of 0.01 to 10 μm. The thickness of the gravure printing ink layer is preferably 0.01 to 10 μm, more preferably 0.1 to 5 μm, and even more preferably 1 to 3 μm. If it is less than 0.1 μm, it is difficult to obtain sufficient density, and if it is greater than 10 μm, it is difficult to form the gravure printing ink layer and the blocking resistance is poor.

[0054] In the method for producing a sulfur-based compound adsorbent laminate of the present invention, in a configuration in which a gravure printing ink layer is laminated, it is preferable that the sulfur-based compound adsorbent layer is formed over an area of ​​10% to 99%, more preferably over an area of ​​20% to 80%, and even more preferably over an area of ​​30% to 60%, when the total area of ​​the surface forming the adsorbent layer is taken as 100%. By ensuring that the formation area of ​​the sulfur-based compound adsorption layer is within the specified range, even when overprinted with the gravure printing ink layer, good blocking resistance is achieved, residual solvents are reduced, and odors from the printed material are also reduced.

[0055] The method for producing the sulfur-based compound adsorbent laminate of the present invention preferably includes a lamination step to create a laminate layer. As an adsorbent laminate, the greater the lamination strength, the better the lamination performance. A lamination strength of 80g or more is sufficient for application, eliminating the risk of insufficient seal strength during bag making. When the contents are placed inside and the bag is used as packaging, it reduces the likelihood of the bag tearing due to dropping during the distribution process and the difficulty of opening the bag for the consumer.

[0056] It is more preferable that the laminating step is a laminating step that forms a sealant layer or a coating step that forms a seal layer. Alternatively, the laminating step may be a laminating step that forms at least one laminate layer from among the dry laminating method, the non-solvent laminating method, the thermal laminating method, the extrusion laminating method, the co-extrusion laminating method, and the PE sandwich laminating method.

[0057] The lamination process for forming the sealant layer may include, for example, lamination of a heat-sealable laminate or a known sealant film, resin coating by extrusion lamination or co-extrusion, and the coating process for forming the sealant layer may include coating with a heat sealant or hot melt agent.

[0058] When using adhesives in lamination processes such as the dry lamination method, non-solvent lamination method, wet lamination method, and extrusion lamination method, commercially available adhesives are acceptable. Examples include two-component or one-component urethane resin adhesives, acrylic, epoxy, polyester, polyethyleneimine, polybutadiene, water-based urethane, isocyanate, organotitanium, starch-based water-soluble adhesives, and water-based adhesives such as vinyl acetate emulsion. For the adhesive application process to form the sealant layer, known application processes can be used. For example, roll coaters, reverse roll coaters, gravure offset coaters, gravure coaters, microgravure coaters, knife coaters, bar coaters, wire bar coaters, die coaters, and dip coaters can be used. There are no particular restrictions on the thickness of the adhesive, but a range of approximately 0.001 to 10 μm is preferred, and a range of 0.01 to 5 μm is particularly preferred.

[0059] Examples of resins that can be used in resin coating processes such as the lamination process that forms a laminate layer by the aforementioned extrusion lamination method or co-extrusion lamination method include polyethylene resins such as LDPE, LLDPE, and HDPE, polypropylene resins, 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 or fumaric acid, polystyrene resins, and thermoplastic resins such as polybutylene terephthalate resins. These resins can be used individually or in mixtures of two or more types.

[0060] The coating process for forming the aforementioned sealing layer includes the application of heat sealants and hot melting agents. Other examples include the application of adhesives and tacks.

[0061] There are no particular restrictions on the thickness of the sealing layer, but it is preferable that the thickness be 0.01 to 30 μm when applying a heat sealant and 1 to 50 μm when applying a hot melt adhesive.

[0062] 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. The film may be stretched or unstretched, and one or more types may be laminated.

[0063] Examples of the resins used in the heat-sealing agent include thermoplastic resins such as vinylidene chloride, shellacs, rosins, rosin-modified maleic acid resins, rosin-modified phenolic resins, nitrated cotton, cellulose acetate, cellulose acetylpropionate, cellulose acetyl butyrate, chlorinated rubber, cycloadhesive 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. These can be used individually or in combination of two or more types. These resins can be dissolved in a solvent, or dispersed in water as acrylic emulsions, urethane emulsions, ethylene-vinyl alcohol emulsions, polyethylene emulsions, polypropylene emulsions, or ethylene vinyl acetate emulsions.

[0064] The sulfur-based compound adsorbent laminate produced by the method for producing a sulfur-based compound adsorbent laminate of the present invention is preferably cut into 10 cm x 10 cm pieces so that the adsorption layer is within a predetermined formation area range, placed in a bag with hydrogen sulfide in 3 L of air to a gas concentration of 20 ppm, sealed, and left standing at room temperature for 24 hours. In this case, the hydrogen sulfide gas concentration is preferably less than 20 ppm, more preferably less than 10 ppm, and even more preferably less than 5 ppm.

[0065] In the method for producing a sulfur-based compound adsorbent laminate of the present invention, the sulfur-based compound adsorbent layer is preferably formed by a multi-color gravure printing process using a multi-color gravure printing method, which involves printing a gravure ink composition for adsorbing sulfur-based compounds, comprising zinc oxide, at least one resin selected from urethane resin, (meth)acrylic resin, polyamide resin, nitrated cotton, chlorinated polyolefin resin, and vinyl chloride / vinyl acetate copolymer resin, and an organic solvent, to a film thickness of 0.5 to 5 μm.

[0066] The zinc oxide is preferably in granular form, with an average particle size of 0.01 to 10 μm, and more preferably 0.02 to 5 μm. An average particle size of 0.01 to 10 μm maintains the adsorption effect of sulfur compounds and prevents the zinc oxide from settling over time. If the average particle size is smaller than 0.01 μm, the dispersibility is poor, and if the average particle size is larger than 10 μm, the transparency is poor.

[0067] The zinc oxide content in the adsorbent ink composition is preferably 1 to 70% by weight, and more preferably 5 to 50% by weight. If the zinc oxide content is less than 1% by weight, the adsorption of sulfur-based compounds is poor, and if the zinc oxide content is more than 70% by weight, the fluidity is poor.

[0068] The adsorbent ink composition preferably contains at least one resin from among urethane resin, (meth)acrylic resin, polyamide resin, nitrated cotton, chlorinated polyolefin resin, and vinyl chloride / vinyl acetate copolymer resin. The resins can be produced by conventional methods. These resins may be one type or two or more types. Commercially available options 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-based) (all manufactured by Tokyo Ink Co., Ltd.).

[0069] The adsorbent ink composition may also contain other thermoplastic resins in addition to the urethane resin, (meth)acrylic resin, polyamide resin, nitrated cotton, chlorinated polyolefin resin, and vinyl chloride / vinyl acetate copolymer resin. For example, shellacs, rosins, rosin-modified maleic acid resins, rosin-modified phenolic resins, cellulose acetate, cellulose acetylpropionate, cellulose acetyl butyrate, chlorinated rubber, cyclized rubber, polyethylene resins, polypropylene 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, 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, polyphenylene sulfone resins, polyimide resins, polyamideimide resins, amorphous polyarylate resins, polyetheretherketone resins, polyvinyl alcohol resins, ethylene-vinyl alcohol resins, and polylactic acid are preferred. These resins may be of one type or more than one type. Commercially available options include TPH medium, VESTA medium, LRC-NT medium, and KCNT medium (all manufactured by Tokyo Ink Co., Ltd.).

[0070] The content of thermoplastic resins in the adsorbent ink composition, including the urethane resin, (meth)acrylic resin, polyamide resin, nitrated cotton, chlorinated polyolefin resin, vinyl chloride / vinyl acetate copolymer resin, and other thermoplastic resins, is preferably 1 to 30% by weight, and more preferably 3 to 20% by weight, on a solid content basis. If the thermoplastic resin content is less than 1% by weight, the film-forming properties of the adsorbent ink composition are poor, and if the thermoplastic resin content is more than 30% by weight, the fluidity of the adsorbent ink composition is poor, resulting in poor manufacturability.

[0071] The adsorbent ink composition can use organic solvents commonly used in gravure inks. Examples of organic solvents include aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane; alcoholic solvents such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, 1-butanol, 2-butanol, isobutanol, and tert-butanol; esteric 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 monoethyl ether. Examples of glycol ether solvents include ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether, as well as their esterified products. As esterified products, acetate-forms are mainly selected, 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, toluene, ethyl acetate, n-propyl acetate, isopropyl alcohol, propylene glycol monomethyl ether, and methyl ethyl ketone are more preferred from the viewpoint of printability and versatility. These can be used individually or in combination of two types. The organic solvent content in the adsorbent ink composition is preferably in 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 suitability for ink manufacturing will be inferior. If it exceeds 98% by weight, the ink film thickness will become locally uneven, resulting in irregular variations in density (swimming phenomenon) on the printed surface, and the viscosity will be low, which may cause zinc oxide to settle easily.

[0072] The adsorbent ink composition may also contain colorants, inorganic fillers, organic fillers, defoamers, leveling agents, antiblocking agents, waxes, pigment dispersants, antistatic agents, slip agents, plasticizers, tackifiers, and the like. Any known and commonly used substances can be appropriately selected as long as they do not impair the properties of the adsorbent ink composition.

[0073] The aforementioned coloring material may contain a pigment, a dye, or a mixture thereof. Examples of pigments include inorganic pigments such as titanium dioxide, iron oxide, barium sulfate, calcium carbonate, silica, zinc oxide, zinc sulfide, mica, talc, and pearl; 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 individually or in combination of two or more types. Dyes are preferably those that dissolve or disperse in a solvent, and may be used individually or in combination of two or more types. Among these, pigments are preferred from the viewpoint of durability.

[0074] In the method for producing a sulfur-based compound adsorbent laminate of the present invention, the gravure printing ink layer is preferably formed by a multicolor gravure printing process using a multicolor gravure printing method that prints a gravure printing ink containing a resin commonly used in gravure inks. Examples of the resin include polyurethane resins, polyolefin resins, shellacs, rosin-modified maleic acid resins, rosin-modified phenolic resins, cellulose acetate, cellulose acetylpropionate, cellulose acetyl butyrate, chlorinated rubber, cyclized rubber, halogenated vinyl resins (e.g., vinyl chloride resins, fluorine-containing vinyl resins, etc.), polyvinyl acetate, vinyl chloride-vinyl acetate copolymers, polystyrene resins, acrylic resins, acrylic styrene copolymers, polyacrylic acid esters, polyester resins, polyvinylidene chloride resins, ketone resins, polyamide resins, nitrocellulose resins, rosin resins, styrene maleic acid resins, alkyd resins, and ethylene-vinyl alcohol resins.

[0075] The resin is preferably present in the gravure ink in a solid content of 1 to 70% by mass, more preferably 2 to 65% by mass, and even more preferably 3 to 60% by mass. If the content is less than 1% by mass, sufficient adhesion cannot be obtained, and if it is more than 70% by mass, the solid content is too high, the viscosity becomes high, and application becomes difficult.

[0076] In addition to resin, the gravure ink may also contain colorants, solvents, inorganic fillers, organic fillers, defoamers, leveling agents, antiblocking agents, waxes, pigment dispersants, antistatic agents, slip agents, plasticizers, tackifiers, antioxidants, surfactants, UV absorbers, surface modifiers, pH adjusters, charge imparters, bactericides, deodorants, wetting agents, anti-skinning agents, metal chelating agents, and the like.

[0077] The aforementioned colorant may contain pigments, dyes, or mixtures thereof. Examples of pigments include inorganic pigments such as titanium dioxide, iron oxide, barium sulfate, calcium carbonate, silica, zinc oxide, zinc sulfide, mica, talc, pearl, aluminum, and carbon black; organic pigments such as phthalocyanine-based, insoluble azo-based, condensed azo-based, dioxazine-based, anthraquinone-based, quinacridone-based, perylene-based, perinone-based, and thioindigo-based pigments; and various other fluorescent pigments, metal powder pigments, and extender pigments. These pigments may be used individually or in combination of two or more types. Dyes are preferably those that dissolve or disperse in a solvent, and may be used individually or in combination of two or more types. Among these, pigments are preferred from the viewpoint of durability. Because it contains a colorant, it is very useful in terms of providing color variations and multi-color images.

[0078] The solvent is used to provide appropriate fluidity and adjust viscosity during the formation of the printed layer, and preferably dissolves or disperses the resin in the solvent.

[0079] Examples of the aforementioned solvents include aromatic hydrocarbon solvents such as water, toluene, and xylene; aliphatic hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane; alcoholic solvents such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, 1-butanol, 2-butanol, isobutanol, and tert-butanol; esteric 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 monoethyl ether. Examples 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 their esterified products. As esterified products, acetate-forms are mainly selected, 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. These can be used individually or in combination of two types.

[0080] The solvent is preferably present in the gravure ink at a concentration of 1 to 90% by mass, more preferably 5 to 80% by mass, and even more preferably 10 to 70% by mass. If the concentration is less than 1% by mass, sufficient printability cannot be obtained, and if it is more than 90% by mass, the solid content will decrease, reducing the adhesion between the substrate and the sulfur-based compound adsorbent layer.

[0081] Examples of commercially available gravure inks include the LG-FK series (urethane resin) and the NOPL-T series (olefin-based) (both manufactured by Tokyo Ink Co., Ltd.).

[0082] The method for producing the sulfur-based compound adsorbent laminate of the present invention preferably includes a step of preparing a substrate. The step of preparing the substrate preferably includes preparing at least one selected from paper, plastic film or sheet, and laminates thereof. For example, as the plastic film, 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 in the middle; polycarbonate films; polyacrylonitrile films; polyimide films; cellophane; moisture-proof cellophane; transparent vapor-deposited polyester films or transparent vapor-deposited polyamide films having a vapor-deposited layer of alumina or silica on PET film or polyamide film; various coated films coated with polyvinylidene chloride resin, polyvinyl alcohol resin, polyacrylic acid resin, etc.; co-extruded films of PET and nylon; polylactic acid films, etc. can be selected and prepared. These can be stretched or unstretched, and the process may involve preparing a laminate of one or more types. Appropriate materials can be selected and prepared considering mechanical strength, dimensional stability, etc. Furthermore, to improve the adhesion of the anchor coat layer and laminate layer to the printing surface, corona treatment, low-temperature plasma treatment, flame treatment, solvent treatment, coating treatment, etc., can be applied, or pre-treated materials can be selected and prepared. Among these, PET film, polyethylene film, polypropylene film, polyamide film, coated film, transparent vapor-deposited polyester film or transparent vapor-deposited polyamide film, and co-extruded film are preferred. The thickness of the substrate is not particularly limited as long as it does not impede printability or winding suitability, but 5 to 300 μm is preferred, and 6 to 250 μm is more preferred. Alternatively, a heat-sealable film such as polyethylene film can be prepared to function as a sealant layer.

[0083] It is preferable to prepare at least one of the following as the paper substrate: coated paper, uncoated paper, and paper substrates obtained by laminating the same to a plastic film, etc. The paper substrate may be prepared by laminating thermoplastic resins, etc., by methods such as dry lamination, non-solvent lamination, or extrusion lamination, or by lamination via an adhesive, etc., or by selecting and preparing a combination of these as appropriate. In addition, laminates to which heat sealability has been imparted by a lamination process to form the sealant layer, laminates to which heat sealability has been imparted by lamination of known sealant films, resin coating by extrusion lamination or co-extrusion, etc., and laminates to which heat sealability has been imparted by a coating process to form a seal layer, such as coating with a heat sealant or hot melt agent, etc., may also be prepared as paper substrates. The thickness of the paper substrate is not particularly limited as long as it does not impede printability, winding suitability, etc., but 5 to 800 μm is preferred, and 6 to 600 μm is more preferred.

[0084] The present invention provides a method for producing a sulfur-based compound adsorbent laminate, which can be configured, for example, as follows: substrate / gravure printing ink layer / sulfur-based compound adsorbent layer / laminate layer; substrate / sulfur-based compound adsorbent layer / gravure printing ink layer / laminate layer; laminate layer (polyethylene sealant) / sulfur-based compound adsorbent layer / gravure printing ink layer; or laminate layer (polyethylene sealant) / gravure printing ink layer / sulfur-based compound adsorbent layer. Furthermore, the method may include a step of forming an intermediate layer to impart or enhance properties such as rigidity, stiffness, gas barrier properties, fragrance retention, moisture resistance, pinhole resistance, dead hole resistance, light shielding properties, and straight cut properties. If the method includes a step of forming an intermediate layer, there are no restrictions on its position. However, in the step of providing a gas barrier layer to impart gas barrier properties, it is preferable that the gas barrier layer is not provided on the side of the sulfur-based compound adsorbent layer formed by the step of forming the sulfur-based compound adsorbent layer that is closer to the source of the adsorbed substance.

[0085] As the intermediate layer, plastic films, sheets, and laminates thereof can be selected and prepared. As plastic films, 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 in the middle; polycarbonate films; polyacrylonitrile films; polyimide films; cellophane; moisture-proof cellophane; transparent vapor-deposited polyester films or transparent vapor-deposited polyamide films with a vapor-deposited layer of alumina or silica on PET film or polyamide film; various coated films coated with polyvinylidene chloride resin, polyvinyl alcohol resin, polyacrylic acid resin, etc.; co-extruded films of PET and nylon; and polylactic acid films can be selected and prepared. These may be stretched or unstretched, and one or more types may be laminated. Appropriate materials can be selected considering mechanical strength and dimensional stability. To improve adhesion, the bonding surfaces can be treated with corona treatment, low-temperature plasma treatment, flame treatment, solvent treatment, coating, or pre-treated surfaces can be selected and prepared. Treatment of both sides is preferable. The intermediate layer can be any thickness that does not impair printability, winding suitability, etc., with a thickness of 5 to 300 μm being preferred, and a thickness of 6 to 250 μm being more preferred.

[0086] The present invention relates to a packaging bag that includes a sulfur-based compound adsorption layer with a thickness of 0.5 to 5 μm, a gravure printing ink layer with a thickness of 0.01 to 10 μm, and a sealant layer or sealing layer. The sulfur-based compound adsorption layer covers 10% to 99% of the total surface area of ​​the surface forming the adsorption layer, and the sulfur-based compound adsorption layer is made of a gravure ink composition for adsorbing sulfur-based compounds, which includes zinc oxide, at least one resin from among urethane resin, (meth)acrylic resin, polyamide resin, nitrated cotton, chlorinated polyolefin resin, and vinyl chloride / vinyl acetate copolymer resin, and an organic solvent. When contents containing a sulfur compound are placed in the packaging bag, the opening is sealed by heat sealing at 190°C for 1 second, and then left to stand at 50°C for 24 hours, it is preferable that there is no sulfurous odor. The packaging bag can also be preferably used as a packaging bag for heat treatment, which is suitable for heat treatment.

[0087] The packaging bag of the present invention preferably comprises a sulfur-based compound adsorption layer with a thickness of 0.5 to 5 μm, and more preferably 0.3 to 3 μm. If the thickness is less than 0.5 μm, the adsorption capacity of sulfur-based compounds decreases. If the thickness is greater than 5 μm, the blocking resistance is poor. The sulfur-based compound adsorption layer is preferably formed by coating using a multi-color gravure printing method.

[0088] The packaging bag of the present invention preferably has a gravure printing ink layer with a film thickness of 0.01 to 10 μm laminated to it. The thickness of the gravure printing ink layer is preferably 0.01 to 10 μm, more preferably 0.1 to 5 μm, and even more preferably 1 to 3 μm. If it is less than 0.1 μm, it is difficult to obtain sufficient density, and if it is greater than 10 μm, it is difficult to form the gravure printing ink layer and the blocking resistance is poor. The gravure printing ink layer is preferably formed by coating using a multi-color gravure printing method.

[0089] In the packaging bag of the present invention, the sulfur-based compound adsorption layer is preferably formed over an area of ​​10% to 99%, more preferably over an area of ​​20% to 80%, and even more preferably over an area of ​​30% to 60%, when the total area of ​​the surface forming the adsorption layer is taken as 100%. By ensuring that the formation area of ​​the sulfur-based compound adsorption layer is within the specified range, even when overprinted with the gravure printing ink layer, good blocking resistance is achieved, residual solvents are reduced, and odors from the printed material are also reduced.

[0090] The packaging bag of the present invention preferably does not emit a sulfurous odor when filled with contents containing a sulfur compound, sealed by heat sealing at 190°C for 1 second, and then left to stand at 50°C for 24 hours. The sealant layer or sealing layer is the innermost layer, and the bag is heat-sealed on three or two sides at 190°C for 1 second. The contents containing the sulfur compound are then placed inside the opening, and the opening is sealed at 190°C for 1 second. The bag is then left to stand at 50°C for 24 hours. After 24 hours, the bag is opened and checked for the presence of a sulfurous odor. It is preferable that there is no sulfurous odor after 24 hours, but it is more preferable that the bag containing the contents prepared under the same conditions is opened and checked for the presence of a sulfurous odor after 4 hours, 8 hours, and 16 hours, and that the sulfurous odor is not detected in the shortest time.

[0091] Furthermore, the packaging bag of the present invention is a packaging bag that requires a sulfur-based compound adsorption layer with a film thickness of 0.5 to 5 μm, a gravure printing ink layer with a film thickness of 0.01 to 10 μm, and a sealant layer or sealing layer, wherein the sulfur-based compound adsorption layer covers an area of ​​10% to 99% of the total surface area forming the adsorption layer, and the sulfur-based compound adsorption layer is a layer made of a gravure ink composition for adsorbing sulfur-based compounds containing zinc oxide, at least one resin from among urethane resin, (meth)acrylic resin, polyamide resin, nitrated cotton, chlorinated polyolefin resin, and vinyl chloride / vinyl acetate copolymer resin, and an organic solvent, and it is preferable that there is no sulfurous odor when the contents containing a sulfur compound are placed in the packaging bag, the opening is sealed by heat sealing at 190°C for 1 second, and then left to stand at 25°C for 48 hours. This packaging bag can be preferably used as a non-heat-treated packaging bag that does not require heat treatment.

[0092] The packaging bag of the present invention preferably comprises a sulfur-based compound adsorption layer with a thickness of 0.5 to 5 μm, and more preferably 0.3 to 3 μm. If the thickness is less than 0.5 μm, the adsorption capacity of sulfur-based compounds decreases. If the thickness is greater than 5 μm, the blocking resistance is poor. The sulfur-based compound adsorption layer is preferably formed by coating using a multi-color gravure printing method.

[0093] The packaging bag of the present invention preferably has a gravure printing ink layer with a film thickness of 0.01 to 10 μm laminated to it. The thickness of the gravure printing ink layer is preferably 0.01 to 10 μm, more preferably 0.1 to 5 μm, and even more preferably 1 to 3 μm. If it is less than 0.1 μm, it is difficult to obtain sufficient density, and if it is greater than 10 μm, it is difficult to form the gravure printing ink layer and the blocking resistance is poor. The gravure printing ink layer is preferably formed by coating using a multi-color gravure printing method.

[0094] In the packaging bag of the present invention, the sulfur-based compound adsorption layer is preferably formed over an area of ​​10% to 99%, more preferably over an area of ​​20% to 80%, and even more preferably over an area of ​​30% to 60%, when the total area of ​​the surface forming the adsorption layer is taken as 100%. By ensuring that the formation area of ​​the sulfur-based compound adsorption layer is within the specified range, even when overprinted with the gravure printing ink layer, good blocking resistance is achieved, residual solvents are reduced, and odors from the printed material are also reduced.

[0095] The packaging bag of the present invention preferably does not emit a sulfurous odor when filled with contents containing a sulfur compound, sealed by heat sealing at 190°C for 1 second, and then left to stand at 25°C for 48 hours. The sealant layer or sealing layer is the innermost layer, and the bag is heat-sealed on three or two sides at 190°C for 1 second. The contents containing the sulfur compound are then placed inside the opening, and the opening is sealed at 190°C for 1 second. The bag is then left to stand at 25°C for 48 hours. After 48 hours, the bag is opened and checked for the presence of a sulfurous odor. It is preferable that there is no sulfurous odor after 48 hours, but it is more preferable that the bag containing the contents prepared under the same conditions is opened and checked for the presence of a sulfurous odor after 12 hours, 24 hours, and 36 hours, and that the sulfurous odor is not detected in the shortest time.

[0096] In the packaging bag of the present invention, it is preferable that the sulfur compound adsorption layer is made of a gravure ink composition for adsorbing sulfur compounds, characterized by containing zinc oxide, at least one resin from among urethane resin, (meth)acrylic resin, polyamide resin, nitrated cotton, chlorinated polyolefin resin, and vinyl chloride / vinyl acetate copolymer resin, and an organic solvent.

[0097] The aforementioned zinc oxide has low toxicity, is readily available, and reacts with sulfur compounds such as hydrogen sulfide, which cause odors, to produce zinc sulfide. The resulting zinc sulfide is white and has little effect on the appearance of transparent substrates, making it useful.

[0098] The zinc oxide is preferably in granular form, with an average particle size of 0.01 to 10 μm, and more preferably 0.02 to 5 μm. An average particle size of 0.01 to 10 μm maintains the adsorption effect of sulfur compounds and prevents the zinc oxide from settling over time. If the average particle size is smaller than 0.01 μm, the dispersibility is poor, and if the average particle size is larger than 10 μm, the transparency is poor. The average particle size referred to here is the D50 particle size measured by laser diffraction / scattering. Examples include the laser diffraction / scattering particle size distribution analyzer LA-920 (manufactured by Horiba, Ltd.) and the MICROTRAC 9320-X100 (manufactured by Honeywell).

[0099] The zinc oxide content in the adsorbent ink composition is preferably 1 to 70% by weight, and more preferably 5 to 50% by weight. If the zinc oxide content is less than 1% by weight, the adsorption of sulfur-based compounds is poor, and if the zinc oxide content is more than 70% by weight, the fluidity is poor.

[0100] The adsorbent ink composition preferably contains at least one resin from among urethane resin, (meth)acrylic resin, polyamide resin, nitrated cotton, chlorinated polyolefin resin, and vinyl chloride / vinyl acetate copolymer resin. The resins can be produced by conventional methods. These resins may be one type or two or more types. Commercially available options 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-based) (all manufactured by Tokyo Ink Co., Ltd.).

[0101] The adsorbent ink composition may also contain other thermoplastic resins in addition to the urethane resin, (meth)acrylic resin, polyamide resin, nitrated cotton, chlorinated polyolefin resin, and vinyl chloride / vinyl acetate copolymer resin. For example, shellacs, rosins, rosin-modified maleic acid resin, rosin-modified phenolic resin, cellulose acetate, cellulose acetylpropionate, cellulose acetyl butyrate, chlorinated rubber, cyclized rubber, polyethylene resin, polypropylene resin, vinyl chloride / vinyl acetate copolymer resin, vinyl chloride resin, ethylene-(meth)acrylic acid copolymer, polyester resin, polyvinylidene chloride resin, vinyl acetate resin, ketone resin, butyral resin, chlorinated ethylene vinyl acetate resin, ethylene vinyl acetate resin, styrene maleic acid resin, polystyrene resin Fat, polyacetal resin, polycarbonate resin, casein, alkyd resin, acrylonitrile resin, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polysulfone resin, polyether resin, polyethersulfone resin, polyetherketone resin, modified polyphenylene ether resin, polyphenylene sulfone resin, polyimide resin, polyamideimide resin, amorphous polyarylate resin, polyetheretherketone resin, polyvinyl alcohol resin, ethylene-vinyl alcohol resin, polylactic acid, etc. are preferred. These resins may be one type or two or more types. Commercially available options include TPH medium, VESTA medium, LRC-NT medium, and KCNT medium (all manufactured by Tokyo Ink Co., Ltd.).

[0102] The content of thermoplastic resins in the adsorbent ink composition, including the urethane resin, (meth)acrylic resin, polyamide resin, nitrated cotton, chlorinated polyolefin resin, vinyl chloride / vinyl acetate copolymer resin, and other thermoplastic resins, is preferably 1 to 30% by weight, and more preferably 3 to 20% by weight, on a solid content basis. If the thermoplastic resin content is less than 1% by weight, the film-forming properties of the adsorbent ink composition are poor, and if the thermoplastic resin content is more than 30% by weight, the fluidity of the adsorbent ink composition is poor, resulting in poor manufacturability.

[0103] The adsorbent ink composition can use organic solvents commonly used in gravure inks. Examples of organic solvents include aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane; alcoholic solvents such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, 1-butanol, 2-butanol, isobutanol, and tert-butanol; esteric 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 monoethyl ether. Examples of glycol ether solvents include ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether, as well as their esterified products. As esterified products, acetate-forms are mainly selected, 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, toluene, ethyl acetate, n-propyl acetate, isopropyl alcohol, propylene glycol monomethyl ether, and methyl ethyl ketone are more preferred from the viewpoint of printability and versatility. These can be used individually or in combination of two types. The organic solvent content in the adsorbent ink composition is preferably in 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 suitability for ink manufacturing will be inferior. If it exceeds 98% by weight, the ink film thickness will become locally uneven, resulting in irregular variations in density (swimming phenomenon) on the printed surface, and the viscosity will be low, which may cause zinc oxide to settle easily.

[0104] The adsorbent ink composition may also contain colorants, inorganic fillers, organic fillers, defoamers, leveling agents, antiblocking agents, waxes, pigment dispersants, antistatic agents, slip agents, plasticizers, tackifiers, and the like. Any known and commonly used substances can be appropriately selected as long as they do not impair the properties of the adsorbent ink composition.

[0105] The aforementioned coloring material may contain a pigment, a dye, or a mixture thereof. Examples of pigments include inorganic pigments such as titanium dioxide, iron oxide, barium sulfate, calcium carbonate, silica, zinc oxide, zinc sulfide, mica, talc, and pearl; 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 individually or in combination of two or more types. Dyes are preferably those that dissolve or disperse in a solvent, and may be used individually or in combination of two or more types. Among these, pigments are preferred from the viewpoint of durability.

[0106] The aforementioned packaging bag may be any of the well-known forms, such as two-side seals, three-side seals, four-side seals, pillow seals, standing pouches, envelope seals, gussets, or heat-sealed seals.

[0107] The adsorbent ink composition can be manufactured by known methods by uniformly dissolving or dispersing at least one resin from among zinc oxide, urethane resin, (meth)acrylic resin, polyamide resin, nitrated cotton, chlorinated polyolefin resin, and vinyl chloride / vinyl acetate copolymer resin, along with a colorant and various additives, in an organic solvent. Dissolution or dispersion can be carried out using various stirrers or dispersers such as dissolvers, roll mills, ball mills, bead mills, sand mills, attritors, paint shakers, agitators, Henschel mixers, colloid mills, pearl mills, ultrasonic homogenizers, wet jet mills, kneaders, and homomixers. These devices may be used individually or in combination of two or more types. If the adsorbent ink composition contains air bubbles or coarse particles, it is preferable to remove them using known filters or centrifuges, as these can reduce printability and print quality.

[0108] The viscosity of the adsorbent ink composition is not particularly limited, as long as it does not interfere with printing. Considering the suitability of the ink composition for manufacturing and handling used in gravure printing, a viscosity of 10 to 1,000 mPa·s at 25°C is preferable. If it is less than 10 mPa·s, the viscosity is too low, and the zinc oxide tends to settle easily. If it is greater than 1,000 mPa·s, the fluidity is poor, which can cause problems during ink manufacturing or make it difficult to fill the ink containers. In this case, it can be measured using a commercially available viscometer such as a Brookfield viscometer or a cone-plate viscometer.

[0109] The aforementioned adsorbent ink composition is preferably used in gravure printing and can be applied as is. However, depending on the application conditions and application effect, it can be diluted with a diluent solvent using a Zahn Cup #3 (manufactured by Rigosha Co., Ltd.) to adjust the viscosity to the desired level. In this case, the viscosity is preferably 10 to 40 seconds at 25°C. If it is less than 10 seconds, it will be too fluid, and if it is greater than 40 seconds, the transferability during printing will be poor.

[0110] The aforementioned diluent can be any solvent that can be used to adjust the viscosity of the adsorbent ink composition, such as organic solvents, and commercially available solvents can also be used; there are no particular restrictions. Examples of commercially available solvents include TA52 solvent (alcohol-based solvent), PU533 solvent (toluene-containing solvent), PU515 solvent (toluene-free solvent), SL9155 solvent (toluene-free solvent), CN104 solvent (toluene-free solvent), AC372 solvent (toluene-free solvent), PP575 solvent (toluene-containing solvent), SL9164 solvent (non-ketone solvent), and SL9170 solvent (non-ketone solvent) (all manufactured by Tokyo Ink Co., Ltd.).

[0111] During printing, a curing agent may be added to the adsorbent ink composition as needed. Examples of polyisocyanate 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 (Stavio PDI), as well as modified forms of these such as trimethylolpropane trimers, isocyanurates, burettes, and allophanates. These can be used individually or in combination of two or more types. Commercially available examples 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), Mytec Y260A (manufactured by Mitsubishi Chemical Corporation), Coronate HX, Coronate HL, Coronate L (manufactured by Tosoh Corporation), Desmodul N75MPA / X (manufactured by Covestro Japan Inc.), and LG Hardener C (manufactured by Tokyo Ink Co., Ltd.). [Examples]

[0112] 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" refers to parts by mass, and "%" refers to weight percent.

[0113] [Preparation of gravure ink compositions for adsorbing sulfur-based compounds] (Manufacturing Examples 1-9) Sixty parts of LG-FK R medium (urethane resin solution, 20% solids, manufactured by Tokyo Ink Co., Ltd.), 20 parts of zinc oxide (fine particle zinc oxide, 100% solids, D50 average particle size 0.025 μm, manufactured by Teika Co., Ltd.), 15 parts of n-propyl acetate, 5 parts of isopropyl alcohol, and 100 parts of ceramic beads were charged and dispersed in a paint shaker for 1 hour to prepare gravure ink composition G1 for adsorption of sulfur-based compounds (abbreviated as adsorption ink G1). Similarly, adsorption inks G2 to G9, as shown in the formulations in Table 1, were prepared according to manufacturing examples 2 to 9.

[0114] The materials used were as follows: PULPTECC Medium: Polyamide resin solution, 30% solids content, manufactured by Tokyo Ink Co., Ltd. LRC-LAMI Medium: Nitrocellulose resin solution, 20% solids content, manufactured by Tokyo Ink Co., Ltd. SYNA-S Medium: Acrylic resin solution, 20% solids content, manufactured by Tokyo Ink Co., Ltd. NOPL-L Medium: Chlorinated polyolefin resin solution, 15% solids content, manufactured by Tokyo Ink Co., Ltd. LAMREK R Medium: Vinyl chloride copolymer solution, 15% solids content, manufactured by Tokyo Ink Co., Ltd. Zinc oxide (4μm): Calcined zinc oxide, 100% solids, D50 average particle size 4μm, manufactured by Hakusui Tech Co., Ltd.

[0115] [Table 1]

[0116] The following were used as the gravure ink composition. White ink W1: LG-FK630R White (manufactured by Tokyo Ink Co., Ltd.) Yellow ink Y1: LG-FK232R Yellow (manufactured by Tokyo Ink Co., Ltd.) Red ink M1: LG-FK121R Red (manufactured by Tokyo Ink Co., Ltd.) Blue ink C1: LG-FK390R blue (manufactured by Tokyo Ink Co., Ltd.) Black ink K1: LG-FK920R Black (manufactured by Tokyo Ink Co., Ltd.) White ink W2: LRC-LAMI630 white (manufactured by Tokyo Ink Co., Ltd.)

[0117] [Preparation of sulfur-based compound adsorbent prints] (Examples 1-7) Using a gravure proofing machine GRAVO-PROOF (model number: CM-W, manufactured by Nissho Gravure Co., Ltd.), a gravure plate with a semitone section prepared to have a printing area of ​​50% was used. The adsorbent ink G1 from Manufacturing Example 1 was diluted with a solvent (40 parts MEK, 40 parts propyl acetate, 20 parts isopropyl alcohol) and adjusted to a viscosity of 17 seconds using a Zahn cup No. 3. This was then printed onto a 20 μm thick stretched polypropylene film, Pyrene P-2161 (abbreviated as OPP, manufactured by Toyobo Co., Ltd.), to a film thickness of 2.0 μm. Furthermore, white ink W1 was adjusted to a viscosity of 17 seconds in the same manner as above and printed onto a sulfur-based compound adsorbent layer to a film thickness of 1.1 μm, obtaining an adsorbent print PR1 of OPP / adsorbent ink G1 / white ink W1. Similarly, by changing the adsorbent ink and film thickness as shown in Table 2, adsorbent print materials PR2 to PR7 were obtained.

[0118] (Examples 8-10) By reversing the printing order of the absorbent ink G1 and the white ink W1, an absorbent printed material PR8 consisting of OPP / white ink W1 / absorbent ink G1 was obtained in the same manner as in Example 1. Similarly, as shown in Table 2, the film thickness of the white ink was changed to obtain adsorbent print materials PR9 to PR10.

[0119] (Examples 11-12) The gravure plates, which were initially made with a 50% printing area, were replaced with gravure plates made with 10% and 95% printing areas, and adsorbent printed materials PR11 to PR12 of OPP / adsorbent ink G1 / white ink W1 were obtained in the same manner as in Example 1.

[0120] (Comparative Examples 1-2) The film thickness of the adsorbent ink G1 was changed to 0.05 μm, and an adsorbent printed material PR21 consisting of OPP / adsorbent ink G1 / white ink W1 was obtained in the same manner as in Example 1. Similarly, as shown in Table 3, the film thickness of the adsorbent ink G1 was changed to 7.0 μm to obtain the adsorbent printed material PR22.

[0121] (Comparative Examples 3-4) The printing order of the adsorbent ink G1 and the white ink W1 was reversed, and the film thickness of the adsorbent ink was changed to 0.05 μm. Adsorbent printed material PR23 consisting of OPP / white ink W1 / adsorbent ink G1 was obtained in the same manner as in Example 8. Similarly, as shown in Table 3, the film thickness of the adsorbent ink G1 was changed to 6.0 μm to obtain the adsorbent printed material PR24.

[0122] (Comparative Examples 5-6) The gravure plates, which were initially made with a 50% printing area, were replaced with gravure plates made with 5% and 100% (solid) printing areas, and adsorbent printed materials PR25 to PR26 of OPP / adsorbent ink G1 / white ink W1 were obtained in the same manner as in Example 1.

[0123] <Blocking resistance> For the adhesive print material, two pieces were prepared, each measuring 3cm x 3cm immediately after creation. These were then stacked with the printed and unprinted sides facing each other, and incubated at 50°C for 24 hours at 500g / cm². 2 After applying a load, the delamination state and delamination resistance were evaluated when the overlapping portion of the printed and non-printed surfaces was separated. A sample that peeled off without resistance and showed no delamination was judged to be good. Blocking resistance was evaluated on a three-point scale: ○: peeled off without resistance and showed no delamination; △: slight resistance or slight delamination (not a practical problem); ×: high resistance during peeling and delamination was observed.

[0124] <Residual solvent> For the same adsorbent printed material as described above for <blocking resistance>, the sulfur-based compound adsorption layer was cut to a size of 100cm x 100cm so that its area was 50% of the total surface area of ​​the surface forming the adsorption layer (with the total surface area of ​​the surface forming the adsorption layer being set to 100%). This was placed in a barrier packaging bag, sealed, and left at 40°C for 24 hours. The solvent odor was checked immediately after opening the barrier packaging bag and evaluated. A sample with 100% (solid) surface area of ​​the surface formed by the sulfur-based compound adsorption layer was used as a comparison control, and samples with less solvent odor than this were judged to have good residual solvent. Eight experimenters evaluated the results on a three-point scale: ○: all eight felt the solvent odor was low, △: five felt the solvent odor was low, and ×: four or more felt the solvent odor was high or unchanged. Similarly, the same evaluation was performed on absorbent printed materials cut to reduce the area of ​​the absorbent layer to 95%, 35%, and 10%, and the results were comparable.

[0125] (Examples 31-37, Comparative Examples 11-12, and Comparative Examples 17-18) Furthermore, the substrate was changed from the stretched polypropylene film Pyrene P-2161 (abbreviated as OPP, manufactured by Toyobo Co., Ltd.) of Example 1 to a polyethylene terephthalate film E-5102 (abbreviated as PET, manufactured by Toyobo Co., Ltd.) with a thickness of 12 μm, and the adsorbent ink G1 was printed to a film thickness of 2.0 μm to obtain adsorbent print PR31 of PET / adsorbent ink G1 / white ink W1. Similarly, as shown in Tables 4 and 5, the adsorbent ink and film thickness were changed to obtain adsorbent print PR32 to PR37, adsorbent print PR51 to PR52, and adsorbent print PR57 to PR58.

[0126] (Examples 38-40 and Comparative Examples 13-14) By reversing the printing order of the adsorbent ink G1 and the white ink W1, adsorbent print PR38 of PET / white ink W1 / adsorbent ink G1 was obtained in the same manner as in Example 31. Similarly, by changing the film thickness of the white ink or adsorbent ink as shown in Tables 4 and 5, adsorbent print PR39 to PR40 and adsorbent print PR53 to PR54 were obtained, respectively.

[0127] (Examples 41-42 and Comparative Examples 15-16) Gravure plates prepared with a 50% printing area were changed to gravure plates prepared with 10% and 95% printing areas, and adsorbent printed materials PR41 to PR42 of PET / adsorbent ink G1 / white ink W1 were obtained in the same manner as in Example 31. Similarly, as shown in Table 5, gravure plates prepared with 5% and 100% (solid) printing areas were changed to obtain adsorbent printed materials PR55 to PR56.

[0128] (Examples 61-65 and Comparative Examples 21-22) Furthermore, the substrate was changed from the stretched polypropylene film Pyrene P-2161 (abbreviated as OPP, manufactured by Toyobo Co., Ltd.) of Example 1 to the nylon film Emblem ON-RT (abbreviated as NY, manufactured by Unitika Ltd.) with a thickness of 15 μm, and the adsorbent ink G1 was printed to a film thickness of 1.9 μm to obtain adsorbent print PR61 of NY / adsorbent ink G1 / white ink W1. Similarly, as shown in Tables 6 and 7, the adsorbent ink and film thickness were changed to obtain adsorbent print PR62 to PR65 and adsorbent print PR81 to PR82, respectively.

[0129] (Example 71 and Comparative Examples 23-24) Furthermore, the substrate was changed from the stretched polypropylene film Pyrene P-2161 (abbreviated as OPP, manufactured by Toyobo Co., Ltd.) of Example 1 to the 40 μm thick unstretched linear low-density polyethylene film L-4102 (abbreviated as PE, manufactured by Toyobo Co., Ltd.), and the adsorbent ink G2 was printed with a film thickness of 2.0 μm to obtain adsorbent print PR71 of PE / adsorbent ink G2 / white ink W1. Similarly, as shown in Table 7, the film thickness of the adsorbent ink G2 was changed to obtain adsorbent print PR83 to adsorbent print PR84, respectively.

[0130] (Example 72 and Comparative Examples 25-26) Furthermore, the base material is made from stretched polypropylene film with a basis weight of 50 g / m². 2Instead of using the single-sided glossy bleached kraft paper (abbreviated as "paper," manufactured by Oji Materia Co., Ltd.) of the gravure paper, adsorbent ink G3 was printed with a film thickness of 1.9 μm, and then white ink W2 was adjusted to a viscosity of 17 sec as described above, and printed with a film thickness of 1.0 μm on the sulfur compound adsorbent layer to obtain adsorbent print PR72 of paper / adsorbent ink G3 / white ink W2. Similarly, as shown in Table 7, the film thickness of adsorbent ink G3 was changed to obtain adsorbent print PR85 to adsorbent print PR86, respectively.

[0131] (Examples 73 and Comparative Examples 27-28) Furthermore, the substrate was changed from the stretched polypropylene film Pyrene P-2161 (abbreviated as OPP, manufactured by Toyobo Co., Ltd.) of Example 1 to the 18 μm thick unstretched polystyrene film Spirophane SPH (abbreviated as CPS, manufactured by Oishi Sangyo Co., Ltd.), and the adsorbent ink G4 was printed with a film thickness of 2.0 μm to obtain adsorbent print PR73 of CPS / adsorbent ink G4 / white ink W1. Similarly, as shown in Table 7, the film thickness of the adsorbent ink G4 was changed to obtain adsorbent print PR87 to adsorbent print PR88, respectively.

[0132] (Examples 74 and Comparative Examples 29-30) Furthermore, the substrate was changed from the stretched polypropylene film Pyrene P-2161 (abbreviated as OPP, manufactured by Toyobo Co., Ltd.) of Example 1 to the unstretched polypropylene film KT (abbreviated as CPP, manufactured by Sun-Tox Co., Ltd.) with a thickness of 25 μm, and the adsorbent ink G5 was printed with a film thickness of 1.9 μm to obtain adsorbent print PR74 of CPP / adsorbent ink G5 / white ink W1. Similarly, as shown in Table 7, the film thickness of the adsorbent ink G5 was changed to obtain adsorbent print PR89 to adsorbent print PR90, respectively.

[0133] (Examples 101-107 and Comparative Examples 41-42) Each of the 1-6 color printing units of the 8-color gravure printing press (manufactured by Fuji Machinery Industry Co., Ltd.) is fitted with a ceramic doctor (manufactured by Tokyo Seisakusho Co., Ltd.), a laser engraving plate (manufactured by Towa Process Co., Ltd.) with a plate depth of 20 μm, chromium hardness of 1050 Hv / stylus of 130 degrees, and 175 lines (however, for laser engraving plates using absorbent inks, a semitone section is created so that the printing area is 50%), and a finisher roll. The absorbent inks used are G1, black ink K1, cyan ink C1, and red ink. Ink M1, yellow ink Y1, and white ink W1 were each diluted with solvent PU515 (manufactured by Tokyo Ink Co., Ltd.) and adjusted to a viscosity of 15 seconds using a Zahn cup No. 3. Then, adsorbent ink G1 was added to the ink pan of unit 1, black ink K1 to the ink pan of unit 2, blue ink C1 to the ink pan of unit 3, red ink M1 to the ink pan of unit 4, yellow ink Y1 to the ink pan of unit 5, and white ink W1 to the ink pan of unit 6. In all units, the doctor blade pressure was 2 kgf / cm². 2 , drying temperature 60℃, printing pressure 2kg / cm 2 At a printing speed of 200 m / min, a stretched polypropylene film with a thickness of 20 μm, Pylen P-2161 (abbreviated as OPP, manufactured by Toyobo Co., Ltd.), was printed with adsorbent ink G1 to a thickness of 1.9 μm, black ink K1 to a thickness of 1.0 μm, cyan ink C1 to a thickness of 1.0 μm, red ink M1 to a thickness of 1.1 μm, yellow ink Y1 to a thickness of 1.0 μm, and white ink W1 to a thickness of 1.0 μm to obtain an adsorbent printed material PR101 consisting of OPP / adsorbent ink G1 / printed layer / white ink W1. During printing, the viscosity was kept constant using a viscosity controller (manufactured by Meisei Co., Ltd.). Similarly, by changing the adsorbent ink and film thickness as shown in Tables 8 and 9, adsorbent printed materials PR102 to PR107 and adsorbent printed materials PR121 to PR122 were obtained, respectively.

[0134] (Examples 108-109 and Comparative Examples 45-46) Gravure plates prepared with a 50% printing area were changed to gravure plates prepared with 10% and 95% printing areas, and adsorbent printed materials PR108 to PR109 were obtained using OPP / adsorbent ink G1 / printing layer / white ink W1, similar to Example 101. Similarly, as shown in Table 9, gravure plates were changed to those prepared with 5% and 100% (solid) printing areas, and adsorbent printed materials PR125 to PR126 were obtained.

[0135] (Examples 110-112 and Comparative Examples 43-44) Each of the 1-6 color printing units of the 8-color gravure printing press (manufactured by Fuji Machinery Industry Co., Ltd.) is fitted with a ceramic doctor (manufactured by Tokyo Seisakusho Co., Ltd.), a laser engraving plate (manufactured by Towa Process Co., Ltd.) with a plate depth of 20 μm, chromium hardness of 1050 Hv / stylus of 130 degrees, and 175 lines (however, for laser engraving plates using absorbent inks, a semitone section is created so that the printing area is 50%), and a finisher roll. The inks used are black ink K1, cyan ink C1, red ink M1, yellow ink Y1, and white ink W1. Adsorbent ink G1 was diluted with a solvent (40 parts MEK, 40 parts propyl acetate, 20 parts isopropyl alcohol) and adjusted to a viscosity of 15 seconds using a Zahn cup No. 3. Then, black ink K1 was added to the ink pan of unit 1, blue ink C1 to the ink pan of unit 2, red ink M1 to the ink pan of unit 3, yellow ink Y1 to the ink pan of unit 4, white ink W1 to the ink pan of unit 5, and adsorbent ink G1 to the ink pan of unit 6. In all units, the doctor blade pressure was 2 kgf / cm². 2 , drying temperature 60℃, printing pressure 2kg / cm 2 At a printing speed of 200 m / min, a stretched polypropylene film with a thickness of 20 μm, Pylen P-2161 (abbreviated as OPP, manufactured by Toyobo Co., Ltd.), was printed with black ink K1 to a thickness of 1.1 μm, cyan ink C1 to a thickness of 1.0 μm, red ink M1 to a thickness of 1.1 μm, yellow ink Y1 to a thickness of 1.1 μm, white ink W1 to a thickness of 1.1 μm, and adsorbent ink G1 to a thickness of 2.0 μm to obtain adsorbent printed material PR110 consisting of OPP / printed layer / white ink W1 / adsorbent ink G1. During printing, the viscosity was kept constant using a viscosity controller (manufactured by Meisei Co., Ltd.). Similarly, as shown in Table 9, the film thickness of the adsorbent ink G1 was changed to obtain adsorbent printed materials PR111 to PR112 and adsorbent printed materials PR123 to PR124, respectively.

[0136] [Table 2]

[0137] [Table 3]

[0138] [Table 4]

[0139] [Table 5]

[0140] [Table 6]

[0141] [Table 7]

[0142] [Table 8]

[0143] [Table 9]

[0144] [Fabrication of sulfur-based compound adsorbent laminates] In Example 1, Takelac A-969V / A-5 (abbreviated as DL, manufactured by Mitsui Chemicals, Inc.) was coated onto the white ink layer of the adsorbent printed material PR1 using A-Bar OSP-10 (manufactured by OSG System Products Co., Ltd.), and a 30 μm thick unoriented polypropylene film, Pyrene P-1128 (abbreviated as CPP, manufactured by Toyobo Co., Ltd.), was laminated to it. After aging at 40°C for 24 hours, an adsorbent laminate LAM1 consisting of OPP / adsorbent ink G1 / white ink W1 / DL / CPP was obtained. Similarly, by changing the adsorbent printing material as shown in Tables 2 and 3, adsorbent laminates LAM2 to LAM12 and adsorbent laminates LAM21 to LAM26 were obtained, respectively.

[0145] In Example 31, Takelac A-969V / A-5 (abbreviated as DL, manufactured by Mitsui Chemicals, Inc.) was coated onto the white ink layer of the adsorbent printed material PR31 using A-Bar OSP-10 (manufactured by OSG System Products Co., Ltd.), and a 40 μm thick unoriented polyethylene film, Rix L-4102 (abbreviated as LL, manufactured by Toyobo Co., Ltd.), was laminated to it. After aging at 40°C for 24 hours, an adsorbent laminate LAM31 of PET / adsorbent ink G1 / white ink W1 / DL / LL was obtained. Similarly, as shown in Tables 4 and 5, the adsorbent printed material was changed to obtain adsorbent laminates LAM33 to LAM42 and LAM51 to LAM56, respectively.

[0146] Similarly, by replacing the adsorbent print PR31 with the adsorbent print PR32, Takelac A-525 / Takenate A-52 (manufactured by Mitsui Chemicals, Inc.) was coated onto the white ink layer of the adsorbent print PR32 with A-Bar OSP-10 (manufactured by OSG System Products Co., Ltd.), and a 15 μm thick nylon film Emblem ON-RT (abbreviated as NY, manufactured by Unitika Ltd.) and a 60 μm thick unoriented polypropylene film Trefan NO ZK93KM (abbreviated as RetoCP, manufactured by Toray Film Processing Co., Ltd.) were laminated together. After aging at 40°C for 24 hours, an adsorbent laminate LAM32 of PET / adsorbent ink G6 / white ink W1 / DL / NY / DL / RetoCP was obtained. Similarly, as shown in Table 5, the adsorbent printed material was changed to obtain adsorbent laminates LAM57 to LAM58, respectively.

[0147] In Example 61, Takelac A-969V / A-5 (abbreviated as DL, manufactured by Mitsui Chemicals, Inc.) was coated onto the white ink layer of the adsorbent printed material PR61 using A-Bar OSP-10 (manufactured by OSG System Products Co., Ltd.), and a 40 μm thick unoriented polyethylene film, Rix L-4102 (abbreviated as LL, manufactured by Toyobo Co., Ltd.), was laminated to it. After aging at 40°C for 24 hours, an adsorbent laminate LAM61 consisting of NY / adsorbent ink G1 / white ink W1 / DL / LL was obtained. Similarly, as shown in Tables 6 and 7, the adsorbent printed material was changed to obtain adsorbent laminates LAM62 to LAM65 and adsorbent laminates LAM81 to LAM82, respectively.

[0148] In Example 71, the adsorbent printed material PR71 was used as the adsorbent laminate LAM71 because the PE layer of the substrate functions as a laminate layer (heat seal layer). Similarly, as shown in Table 7, the adsorbent printed materials PR83 and PR84 were used as the adsorbent laminates LAM83 and LAM84, respectively.

[0149] In Example 72, corona treatment was performed on the opposite side (paper side) of the adsorbent print PR72 containing sulfur compounds. Using an extrusion laminating machine, low-density polyethylene resin petrocene 204 (abbreviated as LDPE40, manufactured by Tosoh Corporation) was melt-extruded at a line speed of 100 m / min to a thickness of 40 μm and laminated. Furthermore, corona treatment was performed on the white ink layer, and low-density polyethylene resin petrocene LW01 (abbreviated as LDPE, manufactured by Tosoh Corporation) was melt-extruded at a thickness of 20 μm and laminated to obtain an adsorbent laminate LAM72 consisting of LDPE40 / / paper / adsorbent ink G3 / white ink W2 / / LDPE. (" / / " indicates extrusion lamination.) Similarly, as shown in Table 7, the adsorbent printing material was changed to adsorbent laminate LAM85 and adsorbent laminate LAM86, respectively.

[0150] On the white ink layer of the adsorbent printed material PR73 of Example 73, impact-resistant polystyrene resin E640N (abbreviated as HIPS, manufactured by Toyo Polystyrene Co., Ltd.) was melt-extruded using an extrusion laminating machine at a line speed of 100 m / min and laminated to a thickness of 200 μm to obtain an adsorbent laminate LAM73 consisting of CPS / adsorbent ink G4 / white ink W1 / / HIPS. Similarly, as shown in Table 7, the adsorbent printed material was changed to obtain adsorbent laminates LAM87 to LAM88, respectively.

[0151] On the white ink layer of the adsorbent printed material PR74 of Example 74, homopolypropylene resin E111G (abbreviated as PP, MFR = 0.5 g / 10 min, manufactured by Prime Polymer Co., Ltd.) was melt-extruded using an extrusion laminating machine at a line speed of 100 m / min, and laminated to a thickness of 600 μm to obtain an adsorbent laminate LAM74 consisting of CPP / adsorbent ink G5 / white ink W1 / / PP. Similarly, as shown in Table 7, the adsorbent printed material was changed to obtain adsorbent laminates LAM89 to LAM90, respectively.

[0152] In Example 101, Takelac A-969V / A-5 (abbreviated as DL, manufactured by Mitsui Chemicals, Inc.) was coated onto the white ink layer of the adsorbent printed material PR101 using A-Bar OSP-10 (manufactured by OSG System Products Co., Ltd.), and a 30 μm thick unoriented polypropylene film, Pyrene P-1128 (abbreviated as CPP, manufactured by Toyobo Co., Ltd.), was laminated to it. After aging at 40°C for 24 hours, an adsorbent laminate LAM101 was obtained consisting of OPP / adsorbent ink G1 / printing layer / white ink W1 / DL / CPP. Similarly, as shown in Tables 8 and 9, the adsorbent printed material was changed to obtain adsorbent laminates LAM102 to LAM112 and LAM121 to LAM126, respectively.

[0153] <Adsorption properties of sulfur-based compound adsorbent laminates> When the sulfur-based compound adsorption layer of the adsorption laminate LAM1 is considered to have a total surface area of ​​100%, a 10cm x 10cm piece of the adsorption laminate was cut to 50% of that area. This piece was placed in a polyvinyl fluoride bag with a rubber stopper, sealed by heat sealing, and then 3L of air was added through the rubber stopper. Test gas (hydrogen sulfide) was then added to a gas concentration of 20ppm, and the bag was left to stand at room temperature. The gas concentration inside 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 fell below the limit of quantification (1ppm), the measurement was stopped at that point. A blank test was also performed by following the same procedure without the sample piece. The adsorption performance was evaluated by comparing the gas concentration measurements after 24 hours. For samples where the gas concentration fell below the limit of quantification 24 hours earlier and the measurement was stopped, the gas concentration after 24 hours was also recorded. The lower the gas concentration after 24 hours, the better the adsorption performance was judged. The evaluation was done on a 5-point scale: ◎◎: Gas concentration after 24 hours is below the limit of quantification, ◎: Gas concentration after 24 hours is less than 5 ppm, ○: Gas concentration after 24 hours is less than 10 ppm, △: Gas concentration after 24 hours is less than 20 ppm (no practical problem), ×: Gas concentration after 24 hours remains at 20 ppm. In the blank test, the gas concentration after 24 hours remained at 20 ppm.

[0154] <Lamination strength of sulfur-based compound adsorbent laminates> Adsorption laminate LAM1 was cut into 15mm wide strips to form test specimens. These specimens were tested using a universal tensile testing machine (RTE-1210, manufactured by Orientec Co., Ltd.) under T-type peeling conditions at the substrate / sulfur-based compound adsorption layer interface, at a tensile speed of 300mm / min. The maximum load at the time of peeling was measured as the laminate strength. The laminate strength was measured five times, and the average value was used. A higher laminate strength was considered to indicate better lamination properties. The laminate strength was evaluated in three stages: ○: 80g or more, △: 50g or more, less than 80g, and ×: less than 50g. Similar evaluations were also performed on the adsorption laminates LAM2 to LAM12, LAM21 to LAM26, LAM31 to LAM42, LAM51 to LAM58, LAM61 to LAM65, LAM71 to LAM74, LAM81 to LAM90, LAM101 to LAM112, and LAM121 to LAM126.

[0155] <Live Ammunition Testing> When the total surface area of ​​the surface forming the sulfur-based compound adsorption layer is considered to be 100%, the adsorption laminate LAM1 was prepared so that its sealant layer or sealing layer was between 10% and 99%. These laminates were then stacked so that the sealant layer or sealing layer was on the innermost surface, and bonded by heat sealing at 190°C for 1 second to obtain a bag-shaped packaging bag PAC1 with an opening. Boiled eggs were placed in this packaging bag as the contents, and the opening was sealed by heat sealing at 190°C for 1 second. For comparison, a packaging bag made from the same substrate and with the same configuration as the adsorption laminate LAM1, but without the adsorption ink printed on it, was similarly prepared, boiled eggs were placed in it, and it was sealed. Packaging bags PAC1 containing the contents and a control packaging bag were placed in a 50°C constant temperature bath and left to stand for 4, 8, 16, and 24 hours. After opening, the bags were opened, and the sulfurous odor was checked and compared. Bags with a reduced sulfurous odor compared to the control bag (which did not have the absorbent ink printed on it) were judged to have good absorbency. Eight experimenters evaluated the results on a two-point scale: ○: all eight people felt that the sulfurous odor had decreased, and ×: even one person felt that the sulfurous odor was the same. Furthermore, packaging bags PAC1 containing the contents as described above were placed in a 25°C constant temperature bath and left to stand for 12, 24, 36, and 48 hours. After that, they were opened, and the sulfurous odor was checked and compared. Those with a reduced sulfurous odor compared to the control bag without the absorbent ink printed on them were judged to have good absorbency. Eight experimenters evaluated the results on a two-point scale: ○: All eight people felt that the sulfurous odor had decreased, ×: Even one person felt that the sulfurous odor was the same. A similar evaluation was also conducted for packaging bags PAC2 through PAC12. Furthermore, similar evaluations were conducted for packaging bags PAC31 to PAC42 using adsorption laminates with a PET base material, packaging bags PAC61 to PAC65 with a NY base material, packaging bag PAC71 with a PE base material, packaging bag PAC72 with a paper base material, packaging bag PAC73 with a CPS base material, packaging bag PAC74 with a CPP base material, and packaging bags PAC101 to PAC112 using adsorption laminates with 6-color printing. Note that adhesive laminates with inferior adhesive properties or lamination strength were not evaluated using live ammunition testing (indicated as "-" in the table).

[0156] According to Tables 2 to 9, the adsorbent laminate of the present invention, which uses adsorbent inks 1 to 9 from manufacturing examples 1 to 9 and laminates a sulfur-based compound adsorbent layer with an appropriate film thickness range, a gravure printing ink layer with an appropriate film thickness range, and a laminate layer, exhibits good blocking resistance, low residual solvent, and no solvent odor, as well as superior adsorption of sulfur-based compounds and laminate strength, as demonstrated by the results of Examples 1 to 12, 31 to 42, 61 to 74, and 101 to 112. On the other hand, the adsorbent laminates of Comparative Examples 1-6, 11-18, 21-30, and 41-46 clearly exhibited poor blocking resistance or high levels of residual solvent, resulting in a lingering solvent odor. Even if they exhibited good blocking resistance and / or low solvent odor, their adsorption or lamination strength was inferior. Furthermore, in the packaging bags of the embodiments of the present invention, the results of actual packaging tests clearly show that when left to stand at 50°C for 24 hours after heat sealing, the sulfurous odor is reduced compared to the control packaging bags that do not have the absorbent ink printed on them. Also, when left to stand at 25°C for 48 hours after heat sealing, the sulfurous odor is reduced compared to the control packaging bags that do not have the absorbent ink printed on them. Therefore, it is possible to suppress the unpleasant sulfurous compound odor that occurs when contents containing sulfur compounds, such as seafood, meat products, egg products, and rice products, are heat-treated, and also to suppress the unpleasant sulfurous compound odor that occurs from contents containing sulfur compounds that are not heat-treated, such as rice crackers.

Claims

1. In a sulfur-based compound adsorbent laminate comprising a sulfur-based compound adsorbent layer with a thickness of 0.5 to 5 μm formed by coating using a multi-color gravure printing method, a gravure printing ink layer with a thickness of 0.01 to 10 μm formed by coating using a multi-color gravure printing method, and a laminate layer, The sulfur-based compound adsorption layer has an area of ​​10% to 99% of the total surface area forming the adsorption layer, when this total area is taken as 100%. The sulfur-based compound adsorption layer is a layer made of a gravure ink composition for adsorbing sulfur-based compounds, comprising zinc oxide, at least one resin from among urethane resin, (meth)acrylic resin, polyamide resin, nitrated cotton, chlorinated polyolefin resin, and vinyl chloride / vinyl acetate copolymer resin, and an organic solvent. A sulfur-based compound adsorbent laminate characterized in that, when the sulfur-based compound adsorbent laminate cut to 10 cm x 10 cm and hydrogen sulfide in 3 L of air so that the gas concentration is 20 ppm are placed in a bag, sealed, and left to stand at room temperature for 24 hours, the hydrogen sulfide gas concentration is less than 20 ppm.

2. The sulfur-based compound adsorbent laminate according to claim 1, characterized in that the laminate layer is a sealant layer or a sealing layer.

3. The sulfur-based compound adsorbent laminate according to claim 1 or 2, characterized in that the laminate layer is at least one laminate layer selected from dry lamination, non-solvent lamination, heat lamination, extrusion lamination, co-extrusion lamination, and PE sandwich lamination.

4. A method for producing a sulfur-based compound adsorbent laminate, comprising a multicolor gravure printing step and a lamination step, wherein the sulfur-based compound adsorbent laminate is produced by printing a sulfur-based compound adsorbent layer to a film thickness of 0.5 to 5 μm using a multicolor gravure printing method, and a gravure printing ink layer is produced by printing a gravure printing ink to a film thickness of 0.01 to 10 μm using a multicolor gravure printing method, wherein the sulfur-based compound adsorbent laminate is produced by printing a gravure ink composition for adsorbing sulfur-based compounds to a film thickness of 0.5 to 5 μm, and a gravure printing ink layer is produced by printing a gravure printing ink to a film thickness of 0.01 to 10 μm, The sulfur-based compound adsorption layer has an area of ​​10% to 99% of the total surface area forming the adsorption layer, when this total area is taken as 100%. A method for producing a sulfur-based compound adsorbent laminate, characterized in that when the sulfur-based compound adsorbent laminate cut to 10 cm x 10 cm by the above-mentioned manufacturing method and hydrogen sulfide are placed in a bag so that the gas concentration in 3 L of air is 20 ppm, the bag is sealed, and the bag is left standing at room temperature for 24 hours, the hydrogen sulfide gas concentration is less than 20 ppm.

5. The method for producing a sulfur-based compound adsorbent laminate according to claim 4, characterized in that the laminating step is a laminating step for forming a sealant layer or a coating step for forming a seal layer.

6. The method for producing a sulfur-based compound adsorbent laminate according to claim 4 or 5, characterized in that the lamination step is a lamination step that forms at least one laminate layer from among a dry lamination step, a non-solvent lamination step, a heat lamination step, an extrusion lamination step, a co-extrusion lamination step, and a PE sandwich lamination step.

7. In a packaging bag that requires a sulfur-based compound adsorption layer with a thickness of 0.5 to 5 μm, a gravure printing ink layer with a thickness of 0.01 to 10 μm, and a sealant layer or sealing layer, The sulfur-based compound adsorption layer has an area of ​​10% to 99% of the total surface area forming the adsorption layer, when this total area is taken as 100%. The sulfur-based compound adsorption layer is a layer made of a gravure ink composition for adsorbing sulfur-based compounds, characterized by containing zinc oxide, at least one resin from among urethane resin, (meth)acrylic resin, polyamide resin, nitrated cotton, chlorinated polyolefin resin, and vinyl chloride / vinyl acetate copolymer resin, and an organic solvent. A packaging bag characterized in that, when contents containing a sulfur compound are placed in the packaging bag, the opening is sealed by heat sealing at 190°C for 1 second, and then left to stand at 50°C for 24 hours, there is no sulfurous odor.

8. In a packaging bag that requires a sulfur-based compound adsorption layer with a thickness of 0.5 to 5 μm, a gravure printing ink layer with a thickness of 0.01 to 10 μm, and a sealant layer or sealing layer, The sulfur-based compound adsorption layer has an area of ​​10% to 99% of the total surface area forming the adsorption layer, when this total area is taken as 100%. The sulfur-based compound adsorption layer is a layer made of a gravure ink composition for adsorbing sulfur-based compounds, characterized by containing zinc oxide, at least one resin from among urethane resin, (meth)acrylic resin, polyamide resin, nitrated cotton, chlorinated polyolefin resin, and vinyl chloride / vinyl acetate copolymer resin, and an organic solvent. A packaging bag characterized in that, when contents containing a sulfur compound are placed in the packaging bag, the opening is sealed by heat sealing at 190°C for 1 second, and then left to stand at 25°C for 48 hours, there is no sulfurous odor.

Images