JP2022099681A - Gravure ink composition for adsorbing sulfur-based compound, sulfur-based compound adsorption printed matter, laminate, method for manufacturing sulfur-based compound adsorption printed matter, method for manufacturing laminate, packaging bag, and packaging container - Google Patents

Abstract

To provide a gravure ink composition for adsorbing a sulfur-based compound which can suppress an unpleasant sulfur-based compound odor generated when contents containing a sulfur compound, such as meat products including seafood and the like, egg products, rice and rice confections are subjected to a heat treatment, and which enables manufacture of printed matter having printability with a simple process.SOLUTION: Provided is a gravure ink composition for adsorbing a sulfur-based compound, which is used for sulfur-based compound adsorption printed matter which includes a base material, and a sulfur-based compound adsorption layer on at least one side of the base material. The gravure ink composition for adsorbing a sulfur-based compound comprises: zinc oxide; at least one resin of an urethane resin, a (meth)acrylic resin, a polyamide resin, nitrocellulose, a chlorinated polyolefin resin and a vinyl chloride-vinyl acetate copolymer resin; and a solvent.SELECTED DRAWING: None

Description

The present invention relates to an ink composition that suppresses an unpleasant sulfur compound odor generated when a content containing a sulfur compound such as meat products such as fish and shellfish, egg products, rice and rice confectionery is heat-treated.

Sulfur-containing amino acids (cystine, methionine, cysteine, α-lipoic acid, etc.) among the amino acids that make up proteins contained in meat products such as seafood, egg products, rice and confectionery, are boiled or retorted. Generates an unpleasant odor when cooked or cooked (fried). This odor is caused by hydrogen sulfide, methyl sulfide, methyl disulfide, methyl trisulfide, methyl mercaptan, ethyl mercaptan, t-butyl mercaptan, n-propyl mercaptan generated by hydrolysis of sulfur-containing amino acids in the amino acids constituting the above protein. , Derived from sulfur-based compounds such as isopropylmercaptan. Since these odors affect the taste and flavor of foods, various studies have been conducted to suppress them.

In order to suppress such odors, there are methods such as kneading deodorant components into the film and enclosing a desiccant with a deodorant effect together, but there is a risk of accidental ingestion and accidental ingestion, and cost increase. , There are many problems such as not being able to include some foods.

In Patent Document 1, a coating agent containing a zinc compound is applied to the surface of the oxygen gas barrier material and dried to provide a coating layer containing the zinc compound on the surface of the oxygen gas barrier material. , A step of obtaining a packaging material having an oxygen gas permeability of 3 cm ³ (STP) / ^m 2.24 hr · atm or less measured at 20 ° C. and 80% relative humidity (RH), and a retort generated from the contents. A method for manufacturing a package including a step of arranging a coating layer containing the zinc compound on the content side of the oxygen gas barrier material so as to be able to absorb the odor and packaging the content is proposed. It has a function of absorbing retort odor generated from food, and a zinc compound is used as a material having a function of absorbing retort odor. However, since the coating agent containing a zinc compound is applied by a coating method using a coating device and not printed by a gravure printing method using a gravure printing machine, a coating agent coating process is required. It's complicated. In addition, since the composition of the coating agent is unknown, it may not be applicable to gravure printing as it is, and the printability (blocking resistance) may be inferior. Therefore, further studies are being conducted to apply it to gravure printing. You will need it.

Japanese Unexamined Patent Publication No. 2013-018551

Therefore, the present invention can suppress the unpleasant sulfur-based compound odor generated when the contents containing sulfur compounds such as meat products such as seafood, egg products, rice and rice confectionery are heat-treated. It is an object of the present invention to provide a gravure ink composition for adsorbing a sulfur-based compound capable of producing a printed matter having printability by a simple process.

The present inventors contain zinc oxide, at least one resin among urethane resin, (meth) acrylic resin, polyamide resin, vitrified cotton, chlorinated polyolefin resin and vinyl chloride / vinyl acetate copolymer resin, and a solvent. We have found that the above-mentioned problems can be solved by the gravure ink composition for adsorbing sulfur-based compounds, and have completed the present invention.

That is, the present invention
(1) In a sulfur-based compound adsorption gravure ink composition used for a sulfur-based compound adsorption printed matter provided with a base material and a sulfur-based compound adsorption layer on at least one of the base materials.
The gravure ink composition for adsorbing sulfur-based compounds includes zinc oxide (A), urethane resin, (meth) acrylic resin, polyamide resin, nitrified cotton, chlorinated polyolefin resin, and vinyl chloride / vinyl acetate copolymer resin at least. A gravure ink composition for adsorbing a sulfur-based compound, which comprises one resin (b1) and a solvent (C).
(2) The gravure ink composition for adsorbing a sulfur-based compound according to (1), wherein the zinc oxide has an average particle size of 0.01 to 10 μm.
(3) Sulfur obtained by laminating the sulfur-based compound adsorption gravure ink composition according to (1) or (2) on at least one surface of a substrate with an ink layer having a thickness of 0.1 to 5 μm. Sulfur-based compound adsorption printed matter, characterized by forming a sulfur-based compound adsorption layer,
(4) Sulfur obtained by laminating the sulfur-based compound adsorption gravure ink composition according to (1) or (2) on at least one surface of a substrate with an ink layer having a thickness of 0.1 to 5 μm. A laminate characterized by forming a sulfur-based compound adsorption layer and laminating a laminate layer on a substrate on the sulfur-based compound adsorption layer or on a substrate opposite to the sulfur-based compound adsorption layer.
(5) The laminated body according to (4), wherein the laminated layer is a sealant layer or a sealing layer.
(6) The laminate according to (4), wherein the laminated layer is at least one of a dry laminate, a non-solvent laminate, a thermal laminate, an extruded laminate, a coextruded laminate, and a PE sandwich laminate. body,
(7) The process of preparing the base material and
It is characterized by including a gravure printing step of producing a sulfur-based compound adsorption layer obtained by printing the sulfur-based compound adsorption gravure ink composition according to (1) or (2) on at least one of the substrates. Method for manufacturing sulfur-based compound-adsorbed printed matter,
(8) The process of preparing the base material and
Gravure printing for producing a sulfur-based compound adsorption layer formed by printing the sulfur-based compound adsorption gravure ink composition according to (1) or (2) on at least one of the substrates with a film thickness of 0.1 to 5 μm. Process and
A laminating step or a coating step of forming a laminating layer on the sulfur-based compound adsorbing layer or on the substrate opposite to the sulfur-based compound adsorbing layer.
A method for manufacturing a laminate, which comprises
(9) The method for producing a laminate according to (8), wherein the laminating step is a laminating step for forming a sealant layer or a coating step for forming a seal layer.
(10) The laminating step is a laminating step of forming at least one laminating layer among a dry laminating step, a non-solvent laminating step, a thermal laminating step, an extrusion laminating step, a coextrusion laminating step, and a PE sandwich laminating step. The method for producing a laminate according to (8), which is characterized by
(11) In a packaging bag that requires a base material, a sulfur-based compound adsorption layer, and a sealant layer or a seal layer, the sulfur-based compound adsorption layer is the sulfur-based compound adsorption gravure according to (1) or (2). A packaging bag, characterized in that it is formed of an ink composition,
(12) In a packaging container that requires a base material, a sulfur-based compound adsorption layer, and an extruded laminate layer, the sulfur-based compound adsorption layer is the gravure ink composition for sulfur-based compound adsorption according to (1) or (2). A packaging container, characterized by being made of material,
It is about.

According to the present invention, in addition to being able to suppress the unpleasant sulfur-based compound odor generated when the contents containing sulfur compounds such as meat products such as seafood, egg products, rice and rice confectionery are heat-treated. It is possible to provide a gravure ink composition for adsorbing a sulfur-based compound capable of producing a printed matter having printability by a simple step.

Hereinafter, embodiments for carrying out the present invention will be described in detail. It should be noted that the present embodiment is merely one embodiment for carrying out the present invention, and the present invention is not limited to the present embodiment, and various modifications and embodiments are made without departing from the gist of the present invention. Is possible.

In the following description, (meth) acrylic or (meth) acrylate means acrylic and methacrylic, acrylate and methacrylate, respectively.

The gravure ink composition for adsorbing a sulfur-based compound of the present invention (hereinafter, also simply referred to as “adsorption ink composition”) is a sulfur-based compound adsorption having a base material and a sulfur-based compound adsorption layer on at least one of the base materials. In the sulfur-based compound adsorption gravure ink composition used for printed matter, the sulfur-based compound adsorption gravure ink composition includes zinc oxide (A), urethane resin, (meth) acrylic resin, polyamide resin, vitrified cotton, and chlorine. It is preferably composed of at least one resin (b1) of the modified polyolefin resin and the vinyl chloride / vinyl acetate copolymer resin and the solvent (C).

The gravure ink composition for adsorbing sulfur-based compounds of the present invention preferably contains zinc oxide (A). The zinc oxide (A) has low toxicity of zinc and is easily available, and zinc reacts with a sulfur-based compound such as hydrogen sulfide that causes an odor to produce zinc sulfide. The zinc sulfide produced is white and is useful because it has little effect on the appearance of transparent substrates and the like.

The zinc oxide (A) is preferably granular, and the average particle size is preferably 0.01 to 10 μm, more preferably 0.02 to 5 μm. When the average particle size is 0.01 to 10 μm, the effect of adsorbing the sulfur-based compound can be maintained, and there is no possibility that zinc oxide will settle 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 means the D50 particle size by the laser diffraction / scattering method. Examples thereof include a laser diffraction / scattering type particle size distribution measuring device LA-920 (manufactured by HORIBA, Ltd.) and MICROTRAC 9320-X100 (manufactured by Honeywell).

The content of zinc oxide (A) in the adsorption ink composition is preferably 1 to 70% by weight, more preferably 5 to 50% by weight. When the content of zinc oxide is less than 1% by weight, the adsorptivity of the sulfur-based compound is inferior, and when the content of zinc oxide is more than 70% by weight, the fluidity is inferior.

The gravure ink composition for adsorbing sulfur-based compounds of the present invention is a resin (b1) of at least one of urethane resin, (meth) acrylic resin, polyamide resin, vitrified cotton, chlorinated polyolefin resin and vinyl chloride / vinyl acetate copolymer resin. ) Is preferably included. The method for producing these resins may be any conventional method. These resins may be one kind or two or more kinds.
Commercially available products include LG-FK R medium (urethane type), PULPTECC medium (polyamide type), LRC-LAMI medium (nitrified cotton type), SYNA-S medium (acrylic type), NOPL-L medium (chlorinated polyolefin type). ), LAMEREK medium (salt-vinegared vinyl) (all manufactured by Tokyo Ink Co., Ltd.) and the like can be used.

The gravure ink composition for adsorbing a sulfur-based compound of the present invention may contain another thermoplastic resin (b2) in addition to the resin (b1). For example, cellacs, rosins, rosin-modified maleic acid resin, rosin-modified phenol resin, cellulose acetate, cellulose acetylpropionate, cellulose acetylbutyrate, rubber chloride, cyclized rubber, polyethylene resin, polypropylene resin, vinyl chloride / acetic acid. Vinyl 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, polyacetal resin, polycarbonate resin, casein, alkyd resin, acrylonitrile resin, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polysulfone resin, polyether resin, polyethersulfone resin , Polyether ketone resin, modified polyphenylene ether resin, polyphenylene sulfone resin, polyimide resin, polyamideimide resin, amorphous polyarylate resin, polyether ether ketone resin, polyvinyl alcohol resin, ethylene-vinyl alcohol resin, polylactic acid and the like are preferable. These resins may be one kind or two or more kinds.
As a commercially available product, TPH medium, VESTA medium, LRC-NT medium, KCNT medium (all manufactured by Tokyo Ink Co., Ltd.) and the like can be used.

The content of the thermoplastic resin (B) in which the resin (b1) and the other thermoplastic resin (b2) are combined in the adsorption ink composition of the present invention is 1 to 30% by weight in terms of solid content. It is preferably present, and more preferably 3 to 20% by weight. When the content of the thermoplastic resin (B) is less than 1% by weight, the film-forming property of the adsorption ink composition is inferior, and when the content of the thermoplastic resin (B) is more than 30% by weight, the adsorption ink composition The fluidity is poor and the manufacturing suitability is inferior.

In the gravure ink composition for adsorbing sulfur-based compounds of the present invention, a solvent usually used for gravure ink can be used. Examples of the solvent include aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane and ethylcyclohexane, methanol, ethanol, isopropyl alcohol, normal propyl alcohol and 1-butanol. , 2-butanol, isobutanol, tert-butanol and other alcohol solvents, ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate and other ester solvents, acetone. , Methyl ethyl ketone, Methyl isobutyl ketone, Cyclohexanone and other ketone solvents, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether. , Glycol ether-based solvents such as propylene glycol monobutyl ether and esterified products thereof are mentioned, and as the esterified product, mainly acetates are selected, for example, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol. Examples thereof include monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. Of these, toluene, ethyl acetate, n-propyl acetate, isopropyl alcohol, propylene glycol monomethyl ether, methyl ethyl ketone and the like are more preferable from the viewpoint of printability and versatility. These can be used alone or in admixture of two.
The solvent is preferably in the range of 65 to 98% by weight in the adsorption ink composition. If it is less than 65% by weight, the solid content becomes large, the fluidity becomes poor, and the ink production suitability is inferior. There is a risk that light and shade (swimming phenomenon) may occur, the viscosity may decrease, and zinc oxide may easily settle.

The adsorbed ink composition includes coloring materials, inorganic fillers, organic fillers, defoamers, leveling agents, blocking inhibitors, waxes, pigment dispersants, antistatic agents, slip agents, plasticizers, tackifiers and the like. Can also be contained. Any known and commonly used ink composition can be appropriately selected as long as the characteristics of the adsorption ink composition are not impaired.

The coloring material may contain a pigment, a dye, or a mixture thereof.
Examples of pigments include inorganic pigments such as titanium dioxide, petals, barium sulfate, calcium carbonate, silica, zinc oxide, zinc sulfide, mica, talc, and pearl, phthalocyanine, insoluble azo, condensed azo, and dioxazine. Examples thereof include organic pigments such as anthraquinone-based, quinacridone-based, perylene-based, perinone-based, thioindigo-based, and carbon black, various other fluorescent pigments, metal powder pigments, and extender pigments. These pigments may be used alone or in combination of two or more. The dye is preferably one that dissolves or disperses in a solvent, and may be used alone or in combination of two or more. Above all, it is preferable to use a pigment from the viewpoint of durability.

The substrate is preferably at least one selected from paper, plastic films or sheets and laminates thereof. For example, polyester films such as polyethylene terephthalate (PET), polyethylene naphthalate and polybutylene terephthalate, polyolefin films such as polyethylene, polypropylene and ethylene-vinyl acetate, polystyrene films, alcohol films such as ethylene-vinyl alcohol and polyvinyl alcohol, and polyamide films. Alternatively, a transparent vapor-deposited polyester film or transparent film having a barrier layer in the middle, a polycarbonate film, a polyacrylonitrile film, a polyimide film, a cellophane, a moisture-proof cellophane, a PET film, or a polyamide film provided with a vapor-deposited layer such as alumina or silica. Examples thereof include vapor-deposited polyamide films, various coating films coated with polyvinylidene chloride resin, polyvinyl alcohol resin, polyacrylic acid resin and the like, PET and nylon coextruded films, and polylactic acid films. These may be either stretched or unstretched, and one type or two or more types may be laminated. Appropriate ones can be selected in consideration of mechanical strength and dimensional stability. Further, in order to improve the adhesion of the anchor coat layer and the laminate layer on the printed surface, a corona treatment, a low temperature plasma treatment, a frame treatment, a solvent treatment, a coating treatment, or the like can be selected. Among them, PET film, polyethylene film, polypropylene film, polyamide film, coating film, transparent vapor-deposited polyester film or transparent vapor-deposited polyamide film, co-extruded film and the like are preferable. The thickness of the base material is not particularly limited as long as it does not interfere with printability, winding suitability, etc., but is preferably 5 to 300 μm, more preferably 6 to 250 μm. Further, since the base material is a film having a heat-sealing property such as a polyethylene film, the base material itself may function as a sealant layer.

The paper base material preferably contains at least one selected from coated paper, uncoated paper, and a paper base material to which a plastic film or the like is bonded thereto. The paper base material may be one in which a thermoplastic resin or the like is laminated by a method such as dry laminating, non-solvent laminating, extrusion laminating, or a method of laminating via an adhesive or the like, or a combination thereof as appropriate. It may be a thing. Further, a laminate having heat-sealing properties can also be used as a paper base material. Examples of the method for imparting heat-sealing properties include laminating known sealant films, resin coating by extrusion laminating, coating of heat-sealing agents and hot melts, and heat-sealing resin processing by co-extrusion. A layer to which heat-sealing property is imparted by a method is also referred to as a heat-sealing layer. The thickness of the paper substrate is not particularly limited as long as it does not interfere with printability, winding suitability, etc., but is preferably 5 to 800 μm, more preferably 6 to 600 μm.

In the sulfur-based compound adsorption printed matter of the present invention, it is preferable that the sulfur-based compound adsorption gravure ink composition forms a sulfur-based compound adsorption layer formed by laminating an ink layer on at least one surface of a base material. The film thickness of the ink layer is preferably 0.1 to 5 μm, more preferably 0.3 to 3 μm. If it is thinner than 0.1 μm, the adsorptivity is lowered. If it is thicker than 5 μm, the blocking resistance is inferior.

The sulfur-based compound adsorption layer is preferably formed by laminating an ink layer on at least one surface of a base material. The sulfur-based compound adsorption layer is preferably formed by being coated by a gravure printing method. In particular, it is more preferable to be formed by coating by a gravure printing method using a multicolor gravure printing machine. The sulfur-based compound adsorption layer may be an ink layer alone formed by laminating with a sulfur-based compound adsorbing gravure ink composition, but the ink layer and another ink layer laminated with another gravure ink composition may be used. It may be included. Further, since it is formed by coating by a gravure printing method, not only full solid printing but also partial printing and reverse printing are possible. Depending on the final packaging mode, these ink layers may change the arrangement position of the base material for forming these sulfur-based compound adsorption layers, and the formation order of these ink layers and other ink layers may change. There is also. That is, for example, after forming a sulfur-based compound adsorption layer such as a base material / ink layer / other ink layer, another base material is laminated by dry laminating or the like (base material / ink layer / other ink layer / DL). It may be configured as a base material (/ other base material), or after forming a sulfur-based compound adsorption layer such as a base material / another ink layer / ink layer (or a plurality of layers such as an ink layer / another ink layer), it is dried. Another base material may be laminated (base material / other ink layer / ink layer / (other ink layer, etc./) DL / other base material) by laminating or the like. Further, by using a printing machine having a reversing mechanism, it is possible to obtain a sulfur-based compound adsorption printed matter having a structure having various other ink layers. For example, after forming a sulfur-based compound adsorption layer such as a base material / ink layer / other ink layer, it is inverted to form another ink layer, and then another base material is laminated by dry laminating or the like (other). It may be configured as a base material / DL / another ink layer / base material / ink layer / other ink layer / DL / other base material).

In addition to the sulfur-based compound adsorption layer, the sulfur-based compound adsorption printed matter of the present invention has rigidity, waist, gas barrier property, fragrance retention, moisture resistance, pinhole resistance, deadhole property, light-shielding property, linear cut property, etc. An intermediate layer may be laminated to impart or enhance the performance of the above. When the intermediate layer is provided, it is not always necessary to provide the sulfur-based compound adsorption layer on the base material, and the sulfur-based compound adsorption layer may be provided on the intermediate layer. However, it is preferable that the gas barrier layer for imparting gas barrier properties is not provided on the source side of the substance to be adsorbed rather than the sulfur-based compound adsorption layer.

Examples of the intermediate layer include a plastic film, a sheet, and a laminate thereof. Examples of the plastic film 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, and alcohol-based films such as ethylene-vinyl alcohol and polyvinyl alcohol. Barrier polyamide film with a film, polyamide film or barrier layer in the middle, polycarbonate film, polyacrylonitrile film, polyimide film, cellophane, moisture-proof cellophane, PET film or polyamide film with a vapor deposition layer such as alumina or silica. Examples thereof include polyester films or transparent vapor-deposited polyamide films, various coating films coated with polyvinylidene chloride resin, polyvinyl alcohol resin, polyacrylic acid resin and the like, PET and nylon coextruded films, and polylactic acid films. These may be either stretched or unstretched, and one type or two or more types may be laminated. Appropriate ones can be selected in consideration of mechanical strength and dimensional stability. In order to improve the adhesion of the bonded surface, it is possible to select whether to perform corona treatment, low temperature plasma treatment, frame treatment, solvent treatment, coating treatment, or the like. The treatment is preferably double-sided treatment.
The intermediate layer may have a thickness of 5 to 300 μm, more preferably 6 to 250 μm, as long as it does not interfere with printability, winding suitability, and the like.

In the laminate of the present invention, a sulfur-based compound adsorption layer formed by laminating an ink layer on at least one surface of a base material is formed by a sulfur-based compound adsorption gravure ink composition on the sulfur-based compound adsorption layer. Alternatively, it is preferable that the laminated layer is laminated on the base material opposite to the sulfur-based compound adsorption layer. The film thickness of the ink layer is preferably 0.1 to 5 μm, more preferably 0.3 to 3 μm. The laminate layer is preferably a sealant layer or a seal layer. Examples of the sealant layer include a laminated body having a heat-sealing property, a layer obtained by laminating a known sealant film, and a resin coating by an extrusion laminating method. The sealing layer may be, for example, a heat-sealing agent or a hot melt. Examples thereof include a layer formed by coating an agent.

As the sealant layer, as long as the seal strength can be sufficiently secured, the bonding method is appropriately selected according to the base material, application, configuration and the like. For example, bonding a sulfur-based compound adsorption layer on the substrate with a known sealant film via an adhesive (dry laminating method, non-solvent laminating method, wet laminating method), bonding by heat (thermal laminating method). , Resin coating by extrusion laminating method (extrusion laminating method, coextrusion laminating method, PE sandwich laminating method) and the like can be preferably used. A laminated body can be produced by one kind or a combination of these methods.
The thickness of the sealant layer is not particularly limited, but is preferably 2 to 200 μm for the sealant film and 1 to 100 μm for the resin coating by the extrusion laminating method.

Examples of the sealant film include polyethylene, polypropylene, ethylene-vinyl acetate, polyolefin films such as copolymers thereof, co-pressed films and colored films thereof, polystyrene films, polyacrylonitrile films, ethylene-vinyl alcohol resin films and the like. It may be either stretched or unstretched, and one type or two or more types may be laminated.

When the adhesive is used in the dry laminating method, the non-solvent laminating method, the wet laminating method, the extruded laminating method, etc., a commercially available adhesive may be used. Examples thereof include epoxy-based, polyester-based, polyethyleneimine-based, polybutadiene-based, water-based urethane-based, isocyanate-based, organic titanium-based, starch-based water-soluble adhesives, and water-based adhesives such as vinyl acetate emulsions. As a method for applying the adhesive for forming the sealant layer, a known application method can be used, for example, a roll coater, a reverse roll coater, a gravure coater, a microgravure coater, a knife coater, a bar coater, and a wire bar coater. , Die coater, dip coater and the like can be used. The thickness of the adhesive is not particularly limited, but is preferably in the range of 0.001 to 10 μm, and particularly preferably in the range of 0.01 to 5 μm.

Resins that can be used for resin coating by the extrusion laminating method include polyethylene resins such as LDPE, LLDPE, and HDPE, polypropylene resins, ethylene-vinyl acetate copolymers, ionomer resins, ethylene-acrylic acid copolymers, and ethylene-acrylic acid. Ethyl copolymer, ethylene-methyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, polyethylene and polypropylene with maleic acid and fumal Examples thereof include an acid-modified polyolefin resin modified with an acid, a polystyrene resin, a thermoplastic resin such as a polybutylene terephthalate resin, and one or more of these resins may be used.

As the seal layer, as long as the seal strength can be sufficiently secured, the forming method is appropriately selected according to the base material, application, configuration and the like. For example, a heat sealant or a hot melt coating can be preferably used. A laminated body can be produced by one kind or a combination of these methods. The thickness of the seal layer is not particularly limited, but is preferably 1 to 50 μm for hot melt adhesive coating and 0.01 to 30 μm for heat sealant coating.

Examples of heat sealant resins include vinyl acetate, serracs, rosins, rosin-modified maleic acid resins, rosin-modified phenolic resins, nitrified cotton, cellulose acetate, cellulose acetylpropionate, cellulose acetylbutyrate, and chloride. Rubber, cyclized rubber, polyamide resin, vinyl chloride-vinyl acetate copolymer, polyester resin, ketone resin, butyral resin, chlorinated polypropylene resin, chlorinated polyethylene resin, chlorinated ethylene vinyl acetate resin, ethylene vinyl acetate resin, ( Meta) Examples thereof include thermoplastic resins such as acrylic resin, urethane resin, ethylene-vinyl alcohol resin, styrene maleic acid resin, casein, and alkyd resin, and these may be used alone or in combination of two or more. Examples thereof include types in which these resins are dissolved in a solvent, or those dispersed in water such as acrylic emulsions, urethane emulsions, ethylene-vinyl alcohol emulsions, polyethylene emulsions, polypropylene emulsions, and ethylene vinyl acetate emulsions.

Further, it is preferable that the laminated layer is at least one of dry laminate, non-solvent laminate, thermal laminate, extruded laminate, coextruded laminate, and PE sandwich laminate. The laminated layer is produced by at least one laminating method among a dry laminating method, a non-solvent laminating method, a thermal laminating method, and a resin coating by an extrusion laminating method (extrusion laminating method, coextrusion laminating method, and PE sandwich laminating method). be able to.

Resins that can be used for resin coating by the extrusion laminating method include polyethylene resins such as LDPE, LLDPE, and HDPE, polypropylene resins (homopolypoly, random polypropylene, etc.), ethylene-vinyl acetate copolymers, ionomer resins, and ethylene-acrylic acid. Polymers, ethylene-ethyl acrylate copolymers, ethylene-methyl acrylate copolymers, ethylene-methacrylic acid copolymers, ethylene-methyl methacrylate copolymers, ethylene-propylene copolymers, methylpentene polymers, Acid-modified polyolefin resin obtained by modifying polyethylene or polypropylene with maleic acid or fumaric acid, polystyrene resin (general-purpose polystyrene (GPPS), impact-resistant polystyrene (HIPS), foamed styrene (PSP), heat-resistant PSP, etc.), polybutylene terephthalate resin Examples thereof include thermoplastic resins such as, and these resins may be used alone or in combination of two or more.

The sulfur-based compound adsorption printed matter of the present invention is used for packaging, food storage, retort, microwave oven, agriculture, civil engineering, fishing, automobile interior / exterior, marine, daily necessities, building material interior / exterior, and housing. It can be used for installation equipment, medical / medical equipment, medicine, home appliances, furniture, stationery / office supplies, sales promotion, commercial, electrical and electronic industrial use, industrial material use, etc. preferable. Above all, it is more preferable to be used for packaging.

The method for producing a sulfur-based compound adsorption printed matter of the present invention comprises a step of preparing a base material and a sulfur-based compound adsorption layer obtained by printing the gravure ink composition for adsorbing a sulfur-based compound on at least one of the base materials. It is preferable to include a gravure printing step for producing. The film thickness of the sulfur-based compound adsorption layer is preferably 0.1 to 5 μm, more preferably 0.3 to 3 μm. If it is smaller than 0.1 μm, the adsorptivity of the sulfur-based compound decreases. If it is larger than 5 μm, the blocking resistance is inferior.

The method for producing the sulfur-based compound adsorption printed matter may be a sulfur-based compound adsorption layer alone obtained by printing the sulfur-based compound adsorption gravure ink composition, but the sulfur-based compound adsorption layer and another gravure ink composition may be used. It may include a gravure printing step of creating another print layer to be printed, and it is more preferable to make it by a gravure printing step using a multicolor gravure printing machine. Further, a gravure printing machine having a reversing mechanism may be used.

In addition to the sulfur-based compound adsorption layer, an intermediate for imparting or enhancing performance such as rigidity, waist, gas barrier property, fragrance retention property, moisture resistance, pinhole resistance, deadhole property, light shielding property, and linear cut property. It may include a step of forming a layer.

The method for producing a laminate of the present invention comprises a step of preparing a base material and printing the sulfur-based compound adsorbing gravure ink composition on at least one of the base materials with a thickness of 0.1 to 5 μm. A gravure printing step for creating a sulfur-based compound adsorption layer, and a laminating step or a coating step for creating a laminate layer on a substrate on the sulfur-based compound adsorption layer or on a substrate opposite to the sulfur-based compound adsorption layer. It is preferable to include the laminating step, and it is more preferable that the laminating step is a laminating step for forming a sealant layer or the coating step is a coating step for forming a seal layer. Further, even if the laminating step is a laminating step of forming at least one laminating layer among a dry laminating step, a non-solvent laminating step, a thermal laminating step, an extrusion laminating step, a coextrusion laminating step, and a PE sandwich laminating step. good.

Examples of the laminating step of forming the sealant layer include a step of laminating a laminate having heat-sealing property, a known sealant film, and resin coating by extrusion laminating processing, and a coating process for forming the sealant layer. The step may be a step of applying a heat sealant or a hot melt agent.

The packaging bag of the present invention is a packaging bag that requires a base material, a sulfur-based compound adsorption layer, and a sealant layer or a seal layer, and the sulfur-based compound adsorption layer is the sulfur-based compound adsorption gravure ink composition. It is preferably formed.

The packaging bag may be in any of well-known forms such as a two-way seal, a three-way seal, a four-way seal, a pillow seal, a standing pouch, an envelope sticker, a gusset, and a fusing seal.

The packaging container of the present invention is a packaging container in which a base material, a sulfur-based compound adsorption layer, and an extruded laminate layer are indispensable, and the sulfur-based compound adsorption layer is formed of the sulfur-based compound adsorption gravure ink composition. It is preferable that the product is made of sulfur.

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

The gravure ink composition for adsorbing sulfur-based compounds of the present invention can be produced by a known method by uniformly dissolving or dispersing zinc oxide, a thermoplastic resin, a coloring material, various additives and the like in a solvent. Dissolving or dispersing can be done with various stirrers or dispersions 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, homomixers, etc. You can use the machine. These devices may be used alone or in combination of two or more. When the adsorbed ink composition contains bubbles or coarse particles, it is preferable to remove them by using a known filter, centrifuge or the like in order to deteriorate the printability and the quality of the printed matter.

The viscosity of the sulfur-based compound adsorbing gravure ink composition is not particularly limited as long as it does not interfere with printing. Considering the manufacturing aptitude, handling, and the like of the ink composition used in gravure printing, it is preferably 10 to 1,000 mPa · s at 25 ° C. If it is less than 10 mPa · s, the viscosity is too low and zinc oxide tends to settle, and if it is larger than 1,000 mPa · s, the fluidity is poor and the ink production is hindered or the container is filled. It will be difficult. In this case, the measurement can be performed using a commercially available viscometer such as a Brookfield type viscometer or a cone plate type viscometer.

The adsorption ink composition is preferably used for gravure printing and can be coated as it is, but depending on the coating conditions and coating effect, it is used in Zahn Cup # 3 (manufactured by Dilution Co., Ltd.). , It can be adjusted to a desired viscosity and used by diluting it with a diluting solvent. The viscosity in this case is preferably 10 to 40 seconds at 25 ° C. If it is less than 10 seconds, it is easy to swim, and if it is longer than 40 seconds, the transferability at the time of printing becomes worse.

The diluting solvent may be any one as long as it can be used by adjusting the viscosity of the adsorption ink composition, and examples thereof include organic solvents, and commercially available ones can also be used, and there is no particular limitation. Commercially available products include TA52 solvent (alcohol-based solvent), PU533 solvent (toluene-containing solvent), PU515 solvent (non-toluene solvent), SL9155 solvent (non-toluene solvent), CN104 solvent (non-toluene solvent), AC372. Examples thereof include a solvent (non-toluene solvent), PP575 solvent (toluene-containing solvent), SL9164 solvent (non-ketone solvent), SL9170 solvent (non-ketone solvent) (all of which are manufactured by Tokyo Ink Co., Ltd.).

At the time of printing, a curing agent can be added to the adsorption ink composition, if necessary. For example, tolylene diisocyanate, aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 4,4'-dicyclohexyldiisocyanate, Examples thereof include aliphatic diisocyanates such as pentan-1,5-diisocyanate (stavioPDI) and polyisocyanate-based curing agents such as modified products such as trimerylolpropane trimers, isocyanurates, bullets and allophanates thereof. These can be used alone or in admixture of two or more. Commercially available products include 24A-100, 22A-75, TPA-100, TSA-100, TSS-100, TAE-100, TKA-100, P301-75E, E402-808, E405-70B, AE700-. 100, D101, D201, A201H (manufactured by Asahi Kasei Corporation), Mytec Y260A (manufactured by Mitsubishi Chemical Corporation), Coronate HX, Coronate HL, Coronate L (manufactured by Tosoh Co., Ltd.), Desmodur N75MPA / X (Co) Examples include Bestro Japan Co., Ltd.) and LG Hardener C (manufactured by Tokyo Ink Co., Ltd.).

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In the examples and comparative examples, the part represents a mass part and% represents a weight%.

[Preparation of gravure ink composition for adsorbing sulfur compounds]
(Example 1)
LG-FK R medium (solid content 20%, manufactured by Tokyo Ink Co., Ltd.) 60 parts, zinc oxide (fine zinc oxide, solid content 100%, D50 average particle diameter 0.025 μm, manufactured by Teika Co., Ltd.) 20 parts, 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 a gravure ink composition G1 (abbreviation: adsorption ink G1) for adsorbing sulfur-based compounds. .. Similarly, the adsorption inks of Examples 2 to 9 were prepared according to the formulation shown in Table 1.

[Preparation of sulfur-based compound adsorption printed matter]
(Example 10)
A solid plate was used for the gravure calibrator GRAVO-PROOF (product number: CM-W, manufactured by Nissho Gravure Co., Ltd.), and the adsorption ink G1 of Example 1 was diluted with a solvent (MEK 40 parts, propyl acetate 40 parts, isopropyl alcohol 20). Part) at Zahn Cup No. After adjusting the viscosity to 17 seconds in No. 3, printing was performed on Pyrene P-2161 (abbreviation: OPP, manufactured by Toyobo Co., Ltd.) of a stretched polypropylene film having a thickness of 20 μm with a thickness of 1.0 μm to obtain an adsorption printed matter PR1. Similarly, as shown in Table 2, the adsorption ink and the film thickness were changed to obtain adsorption printed matter PR10 to PR14, respectively.

(Example 11)
Further, the substrate was replaced with the polyethylene terephthalate film E-5102 (abbreviation: PET, manufactured by Toyobo Co., Ltd.) having a thickness of 12 μm, and the adsorption ink G1 was printed with a thickness of 1.1 μm to obtain an adsorption printed matter PR2. ..

(Example 12)
Further, the substrate was replaced with the emblem ON-RT (abbreviation: NY, manufactured by Unitika Ltd.) of a nylon film having a thickness of 15 μm, and the adsorption ink G1 was printed with a thickness of 0.9 μm to obtain an adsorption printed matter PR3. ..

(Example 13)
Further, the substrate is replaced with Barrierox 1011HGCR (abbreviation: thin-film PET, manufactured by Toray Film Processing Co., Ltd.), which is a vapor-filmed polyethylene terephthalate film having a thickness of 12 μm. Obtained PR4.

(Example 14)
Further, the substrate is replaced with L-4102 (abbreviation: PE, manufactured by Toyobo Co., Ltd.), which is a non-stretched linear low-density polyethylene film having a thickness of 40 μm, and the adsorption ink G2 is printed with a thickness of 0.9 μm and adsorbed. A printed matter PR5 was obtained. Similarly, as shown in Table 2, the film thickness was changed to obtain adsorption printed matter PR15 to PR16, respectively.

(Example 15)
Further, the base material was replaced with a single-gloss kraft paper (abbreviation: paper, manufactured by Oji Materia Co., Ltd.), which is a gravure paper having a paper density of 50 g / m ² , and the adsorption ink G3 was printed with a film thickness of 1.2 μm. Adsorption printed matter PR6 was obtained. Similarly, as shown in Table 2, the film thickness was changed to obtain adsorption printed matter PR17 to PR18, respectively.

(Example 16)
Further, the substrate was replaced with styrophan SPH (abbreviation: CPS, manufactured by Oishi Sangyo Co., Ltd.), which is an unstretched polystyrene film having a thickness of 18 μm, and the adsorption ink G4 was printed with a thickness of 1.0 μm to obtain an adsorption printed matter PR7. rice field. Similarly, as shown in Table 2, the film thickness was changed to obtain adsorption printed matter PR19 to PR20, respectively.

(Example 17)
Further, the substrate was replaced with KT (abbreviation: CPP, manufactured by Sun Tox Co., Ltd.), which is an unstretched polypropylene film having a thickness of 25 μm, and the adsorption ink G5 was printed with a thickness of 1.0 μm to obtain an adsorption printed matter PR8. rice field. Similarly, as shown in Table 2, the film thickness was changed to obtain adsorption printed matter PR21 to PR22, respectively.

(Example 18)
Further, the substrate was replaced with the polyethylene terephthalate film E-5102 (abbreviation: PET, manufactured by Toyobo Co., Ltd.) having a thickness of 12 μm, and the adsorption ink G6 was printed with a thickness of 0.9 μm to obtain an adsorption printed matter PR9. .. Similarly, as shown in Table 2, the film thickness was changed to obtain adsorption printed matter PR23 to PR24, respectively.

(Comparative Example 1)
The LG-FK R medium used in Example 1 was mixed with a diluting solvent (MEK 40 parts, propyl acetate 40 parts, isopropyl alcohol 20 parts) in Zahn Cup No. After adjusting the viscosity to 17 seconds in No. 3, printing was performed on Pyrene P-2161 (abbreviation: OPP, manufactured by Toyobo Co., Ltd.) of a stretched polypropylene film having a thickness of 20 μm with a thickness of 0.9 μm to obtain an adsorption printed matter PR25.

(Comparative Example 2)
Further, the substrate was replaced with E-5102 (abbreviation: PET, manufactured by Toyobo Co., Ltd.), which is a polyethylene terephthalate film having a thickness of 12 μm, and printed with a film thickness of 1.1 μm in the same manner as in Comparative Example 1, and an adsorption printed matter was printed. Obtained PR26.

(Comparative Example 3)
Further, the substrate was printed with a film thickness of 1.0 μm in the same manner as in Comparative Example 1 in place of the nylon film emblem ON-RT (abbreviation: NY, manufactured by Unitika Ltd.) having a thickness of 15 μm, and the adsorbed printed matter was printed. Obtained PR27.

(Comparative Example 4)
Further, the substrate is replaced with Barrierox 1011HGCR (abbreviation: thin-film PET, manufactured by Toray Film Processing Co., Ltd.), which is a vapor-filmed polyethylene terephthalate film having a thickness of 12 μm, and is printed with a film thickness of 1.1 μm in the same manner as in Comparative Example 1. Then, the adsorption printed matter PR28 was obtained.

(Comparative Example 5)
Further, the substrate was replaced with L-4102 (abbreviation: PE, manufactured by Toyobo Co., Ltd.), which is a non-stretched linear low-density polyethylene film having a thickness of 40 μm, and the PULPTEC medium used in Example 2 was diluted with a solvent (MEK 40 parts). , 40 parts of propyl acetate, 20 parts of isopropyl alcohol) After adjusting the viscosity to 17 seconds in 3, printing was performed with a film thickness of 1.1 μm to obtain an adsorption printed matter PR29.

(Comparative Example 6)
Further, the base material is replaced with a single-gloss kraft paper (abbreviation: paper, manufactured by Oji Materia Co., Ltd.), which is a gravure paper having a paper density of 50 g / m ² , and the LRC-LAMI medium used in Example 3 is used as a diluting solvent. (MEK 40 parts, propyl acetate 40 parts, isopropyl alcohol 20 parts) with Zahn Cup No. After adjusting the viscosity to 17 seconds in 3, printing was performed with a film thickness of 1.1 μm to obtain an adsorption printed matter PR30.

(Comparative Example 7)
Further, the substrate was replaced with styrene SPH (abbreviation: CPS, manufactured by Oishi Sangyo Co., Ltd.), which is an unstretched polystyrene film having a thickness of 18 μm, and the SYNA-S medium used in Example 4 was diluted with a solvent (MEK 40 parts, acetic acid). 40 parts of propyl, 20 parts of isopropyl alcohol) in Zahn Cup No. After adjusting the viscosity to 17 seconds in 3, printing was performed with a film thickness of 1.0 μm to obtain an adsorption printed matter PR31.

(Comparative Example 8)
Further, the base material was replaced with KT (abbreviation: CPP, manufactured by Sun Tox Co., Ltd.) of a non-stretched polypropylene film having a thickness of 25 μm, and NOPL-L medium used in Example 5 was diluted with a solvent (MEK 40 parts, acetic acid). 40 parts of propyl, 20 parts of isopropyl alcohol) in Zahn Cup No. After adjusting the viscosity to 17 seconds in 3, printing was performed with a film thickness of 1.0 μm to obtain an adsorption printed matter PR32.

(Comparative Example 9)
Further, the base material was replaced with E-5102 (abbreviation: PET, manufactured by Toyobo Co., Ltd.) of a polyethylene terephthalate film having a thickness of 12 μm, and the LAMREK medium used in Example 6 was diluted with a solvent (MEK 40 parts, propyl acetate 40 parts). , Isopropyl alcohol 20 parts) in Zahn Cup No. After adjusting the viscosity to 17 seconds in 3, printing was performed with a film thickness of 0.9 μm to obtain an adsorption printed matter PR33.

(Comparative Example 10)
As shown in Table 3, the adsorption ink G1 was used and the film thickness was changed to 0.05 μm in the same manner as in Example 10 to obtain an adsorption printed matter PR34.

(Comparative Example 11)
As shown in Table 3, the adsorption ink G1 was used and the film thickness was changed to 6.0 μm in the same manner as in Example 10 to obtain an adsorption printed matter PR35.

The blocking resistance of the adsorption printed matter of Examples 10 to 33 and Comparative Examples 1 to 11 was evaluated and shown in Tables 2 and 3.

<Blocking resistance>
Cut the adsorption printed matter into a size of 3 cm x 3 cm, superimpose the printed surface and the non-printed surface, apply a load of 500 g / cm ² at 50 ° C. for 24 hours, and then superimpose the printed surface and the non-printed surface. The state of ink peeling when the portion was peeled off was observed, and the peeling resistance at that time was evaluated. It was judged that the one with no ink peeling and no peeling resistance had good blocking resistance. Regarding ink peeling and peeling resistance, ○: No ink peeling and no peeling resistance, Δ: Slight ink peeling was observed and peeling resistance (no problem in practical use), ×: Ink peeling was observed throughout. It was evaluated on a three-point scale with considerable peeling resistance.

[Preparation of laminated body]
Takelac A-969V / A-5 (abbreviation: DL, manufactured by Mitsui Chemicals, Inc.) is coated on the adsorption ink layer of the adsorption printed matter PR1 with A-Bar OSP-10 (manufactured by OSG System Products Co., Ltd.). Then, after laminating Pyrene P-1128 (abbreviation: CPP, manufactured by Toyobo Co., Ltd.), which is a non-stretched polypropylene film having a thickness of 30 μm, aging was performed at 40 ° C. for 24 hours to laminate PR1 / DL / CPP. Body LAM1 was obtained.
Similarly, the adsorption printed matter PR1 was replaced with the adsorption printed matter PR10 to PR14, PR25 and PR34 to obtain laminated matter LAM11 to LAM15, LAM26 and LAM36.

Similarly, the adsorption printed matter PR1 is replaced with the adsorption printed matter PR2, and Takelac A-525 / Takenate A-52 (manufactured by Mitsui Chemicals, Inc.) is coated with A-Bar OSP-10 (manufactured by OSG System Products Co., Ltd.). Then, after adsorbing Trefan NO ZK93KM (abbreviation: Reto CPP, manufactured by Toray Film Processing Co., Ltd.), which is a non-stretched polypropylene film having a thickness of 60 μm, aging is performed at 40 ° C. for 24 hours, and PR2 / DL / A laminated body LAM2 of Leto CPP was obtained.
Similarly, the adsorption printed matter PR1 was replaced with the adsorption printed matter PR26 to obtain a laminated body LAM27.

Similarly, on the adsorption ink layer of the adsorption printed matter PR2, Takelac A-969V / A-5 (abbreviation: DL, manufactured by Mitsui Chemicals, Inc.) is applied with A-Bar OSP-10 (manufactured by OSG System Products Co., Ltd.). After coating, instead of Rix L-4102 (abbreviation: LLDPE, manufactured by Toyobo Co., Ltd.), which is a non-stretched polyethylene film having a thickness of 40 μm, aging was performed at 40 ° C. for 24 hours to laminate PR2 / DL / LLDPE. Body LAM3 was obtained.
Similarly, the adsorption printed matter PR2 was replaced with the adsorption printed matter PR26 to obtain a laminated body LAM28.

Similarly, the adsorption printed matter PR1 is replaced with the adsorption printed matter PR3, and Takelac A-969V / A-5 (manufactured by Mitsui Chemicals Co., Ltd.) is coated with A-Bar OSP-10 (manufactured by OSG System Products Co., Ltd.). After laminating Rix L-4102 (abbreviation: LLDPE, manufactured by Toyobo Co., Ltd.), which is a non-stretched polyethylene film having a thickness of 40 μm, aging was performed at 40 ° C. for 24 hours to obtain a laminate of PR3 / DL / LLDPE. Obtained LAM4.
Similarly, the adsorption printed matter PR1 was replaced with the adsorption printed matter PR27 to obtain a laminated body LAM29.

Similarly, the adsorption printed matter PR1 is replaced with the adsorption printed matter PR4, and Takelac A-525 / Takenate A-52 (manufactured by Mitsui Chemicals, Inc.) is coated with A-Bar OSP-10 (manufactured by OSG System Products Co., Ltd.). Then, instead of Trefan NO ZK93KM (abbreviation: Reto CPP, manufactured by Toray Film Processing Co., Ltd.), which is a non-stretched polypropylene film with a thickness of 60 μm, aging was performed at 40 ° C. for 24 hours, and PR4 / DL / Reto CPP. LAM5 was obtained.
Similarly, the adsorption printed matter PR1 was replaced with the adsorption printed matter PR28 to obtain a laminated body LAM30.

In the adsorption printed matter PR5, since the PE layer of the base material functions as a heat seal layer, the laminated matter LAM6 was used as it was.
Similarly, the adsorption printed matter PR29 was used as it was as the laminated body LAM31.

The opposite surface (on paper) of the adsorption ink layer of the adsorption printed matter PR6 is corona-treated, and a low-density polyethylene resin Petrosen 204 (abbreviation: LDPE40, Tosoh Corporation) is applied at a line speed of 100 m / min with an extrusion laminating machine. Is melt-extruded and laminated at 40 μm, then corona-treated on the adsorption ink layer, and low-density polyethylene resin Petrosen LW01 (abbreviation: LDPE20, manufactured by Tosoh Co., Ltd.) is melt-extruded and laminated at 20 μm. , LDPE20 // PR6 // LDPE40 laminated body LAM7 was obtained. ("//" represents an extruded laminate.)

Similarly, the adsorption printed matter PR6 was replaced with the adsorption printed matter PR17 to PR18 and PR30 to obtain laminated matter LAM18 to LAM19 and LAM32 of LDPE20 // PR17 // LDPE40.

Impact-resistant polystyrene resin E640N (abbreviation: HIPS, manufactured by Toyo Polystyrene Co., Ltd.) is melt-extruded onto the adsorption ink layer of the adsorption printed matter PR7 at a line speed of 100 m / min using an extrusion laminating machine, and laminated at 200 μm. Then, a laminated body LAM8 of PR7 // HIPS was obtained.

Similarly, the adsorption printed matter PR7 was replaced with the adsorption printed matter PR19 to PR20 and PR31 to obtain the laminated matter LAM20 to LAM21 and LAM33 of PR19 // HIPS.

Homopolypropylene resin E111G (abbreviation: PP, MFR = 0.5 g / 10 min, manufactured by Prime Polymer Co., Ltd.) is melted on the adsorbed ink layer of the adsorbed printed matter PR8 at a line speed of 100 m / min using an extrusion laminating machine. It was extruded and laminated at 600 μm to obtain a laminated product LAM9 of PR8 / LD // PP.

Similarly, the adsorption printed matter PR8 was replaced with the adsorption printed matter PR21 to PR22 and PR32 to obtain laminated matter LAM22 to LAM23 and LAM34 of PR21 / LD // PP.

The adsorption ink layer of the adsorption printed matter PR9 is coated with Takelac A-525 / Takenate A-52 (manufactured by Mitsui Chemicals, Inc.) A-Bar OSP-10 (manufactured by OSG System Products Co., Ltd.) to obtain a thickness. After laminating Trefan NO ZK93KM (abbreviation: CPP, manufactured by Toray Film Processing Co., Ltd.), which is a 60 μm unstretched polypropylene film, aging is performed at 40 ° C. for 24 hours, and the laminated body LAM10 of PR9 / DL / CPP is performed. Got

Similarly, the adsorption printed matter PR9 was replaced with the adsorption printed matter PR23 to PR24 and PR33 to obtain the laminated matter LAM24 to LAM25 and LAM35 of PR23 / DL / CPP.

The adsorptivity of the laminated bodies LAM1 to LAM36 was evaluated and shown in Tables 2 and 3. For Comparative Example 11 (PR35) whose blocking resistance was evaluated as "x", the adsorptivity was not evaluated. In Table 3, it is written as "-".

<Adsorption of laminated body>
A sample piece cut into a size of 10 cm × 10 cm was placed in a polyvinyl fluoride bag with a rubber stopper, sealed with a heat seal, and then 3 L of air was sealed from the rubber stopper for further testing. Gas (hydrogen sulfide) was added so that the gas concentration was 20 ppm, and this was allowed to stand at room temperature. The gas concentration in the bag was measured from a rubber stopper at regular time intervals (10 minutes, 1 hour, 3 hours, 6 hours, 24 hours) using a detector tube. When the gas concentration was below the lower limit of quantification (1 ppm), the measurement was terminated at that point. In addition, a blank test was taken by performing the same operation as above without inserting a sample piece. The measured values of the gas concentration after 24 hours were compared to evaluate the adsorptivity. The gas concentration after 24 hours was used for the gas concentration that was below the lower limit of quantification 24 hours before and the measurement was completed. It was judged that the lower the gas concentration after 24 hours, the better the adsorptivity. 〇: The gas concentration after 24 hours was less than 20 ppm, and ×: the gas concentration after 24 hours remained at 20 ppm.

<Cartridge test>
The sealant layer or the seal layer of the laminated body LAM1 is laminated so as to be the innermost surface, and adhered by heat sealing at 190 ° C. for 1 second to obtain a bag-shaped packaging bag having an opening, and this packaging bag is obtained. Boiled eggs were put into the bag, and the opening was sealed with a heat seal at 190 ° C. for 1 second. At this time, as a comparative control, a packaging bag was obtained in the same manner for the laminated body LAM26 (without the adsorption ink printing of the same base material as the laminated body LAM1), and a boiled egg was put in and sealed. In addition, in Table 3, it is described as "-".
Further, the laminated bodies LAM11 to 13 (differently adsorbed ink), LAM14 to 15 and LAM36 (same substrate as the laminated body LAM1 but different adsorbed ink film thickness) were also obtained in the same manner to obtain a packaging bag, and a boiled egg was put in and sealed. ..
These were placed in a constant temperature bath at 50 ° C., allowed to stand for 24 hours, opened, and the sulfur odor was confirmed and compared. It was judged that the one having a reduced sulfur odor had better adsorptivity than the comparative control in which the adsorption ink was not printed. Among the eight experimenters, all of 0: 8 felt that the sulfur odor was reduced, and ×: 1 felt that the sulfur odor was the same, and the evaluation was made on a two-point scale.
Similarly, the same evaluation was performed for the laminated bodies LAM3 and LAM28, LAM4 and LAM29, LAM5 and LAM30, and LAM6 and LAM31.

According to Tables 2 and 3, it was clear that the adsorption inks 1 to 9 of Examples 1 to 9 had good adsorptivity from the results of Examples 10 to 33. Further, it was clear that the adsorption printed matter PR1 to PR24 had good blocking resistance. From the results of Comparative Examples 1 to 9 in which the adsorption ink of the present invention is not used, it is clear that the effect of adsorptivity does not appear. Even if the adsorption ink of the present invention is used, it is clear that if the print film thickness is smaller than the appropriate range (PR34), the effect of adsorptivity does not appear, and if the print film thickness is large, the blocking resistance is reduced. However, it is clear that it cannot be used as a printed matter (PR35), although it may have an adsorptive effect.
Further, in the actual packaging test using the adsorption ink of the present invention, it is clear that the sulfur odor is reduced as compared with the case where the adsorption ink is not used. Furthermore, it is clear that if the film thickness of the print is smaller than the appropriate range, the adsorption effect does not appear.
Therefore, in addition to being able to suppress the unpleasant sulfur-based compound odor generated when the contents containing sulfur compounds such as meat products such as seafood, egg products, rice and rice cakes are heat-treated, a simple process. It is possible to produce printed matter and packaging materials having printability in the above.

Claims (12)

In a sulfur-based compound adsorption gravure ink composition used for a sulfur-based compound adsorption printed matter having a base material and a sulfur-based compound adsorption layer on at least one of the base materials.
The gravure ink composition for adsorbing sulfur-based compounds includes zinc oxide (A), urethane resin, (meth) acrylic resin, polyamide resin, nitrified cotton, chlorinated polyolefin resin, and vinyl chloride / vinyl acetate copolymer resin at least. A gravure ink composition for adsorbing a sulfur-based compound, which comprises one resin (b1) and a solvent (C). The gravure ink composition for adsorbing a sulfur-based compound according to claim 1, wherein the average particle size of zinc oxide is 0.01 to 10 μm. The sulfur-based compound adsorption layer in which the sulfur-based compound adsorption gravure ink composition according to claim 1 or 2 is laminated on at least one surface of a base material with an ink layer having a thickness of 0.1 to 5 μm. A sulfur-based compound adsorption printed matter characterized by being formed. The sulfur-based compound adsorption layer in which the sulfur-based compound adsorption gravure ink composition according to claim 1 or 2 is laminated on at least one surface of a base material with an ink layer having a thickness of 0.1 to 5 μm. A laminated body formed by laminating a laminated layer on a base material on the sulfur-based compound adsorption layer or on a substrate opposite to the sulfur-based compound adsorption layer. The laminated body according to claim 4, wherein the laminated layer is a sealant layer or a sealing layer. The laminate according to claim 4, wherein the laminate layer is at least one of a dry laminate, a non-solvent laminate, a thermal laminate, an extruded laminate, a coextruded laminate, and a PE sandwich laminate. The process of preparing the base material and
Sulfur including a gravure printing step of producing a sulfur-based compound adsorption layer obtained by printing the sulfur-based compound adsorbing gravure ink composition according to claim 1 or 2 on at least one of the substrates. A method for producing an adsorbed printed matter of a system compound. The process of preparing the base material and
A gravure printing step for producing a sulfur-based compound adsorption layer obtained by printing the sulfur-based compound adsorption gravure ink composition according to claim 1 or 2 on at least one of the substrates with a film thickness of 0.1 to 5 μm. ,
A laminating step or a coating step of forming a laminating layer on the sulfur-based compound adsorbing layer or on the substrate opposite to the sulfur-based compound adsorbing layer.
A method for producing a laminate, which comprises. The method for producing a laminate according to claim 8, wherein the laminating step is a laminating step for forming a sealant layer or a coating step for forming a seal layer. The laminating step is characterized in that it is a laminating step for forming at least one laminating layer among a dry laminating step, a non-solvent laminating step, a thermal laminating step, an extrusion laminating step, a co-extruded laminating step, and a PE sandwich laminating step. The method for manufacturing a laminated body according to claim 8. In a packaging bag that requires a base material, a sulfur-based compound adsorption layer, and a sealant layer or a seal layer, the sulfur-based compound adsorption layer is the sulfur-based compound adsorption gravure ink composition according to claim 1 or 2. A packaging bag characterized by being formed. In a packaging container that requires a base material, a sulfur-based compound adsorption layer, and an extruded laminate layer, the sulfur-based compound adsorption layer is formed of the sulfur-based compound adsorption gravure ink composition according to claim 1 or 2. A packaging container characterized by that.