Coated products, laminates, methods for manufacturing coated products and laminates, labels and packaging, and organic solvent-based gravure ink compositions used therein.

Abstract

The present invention reduces the environmental impact by replacing the high-boiling-point solvent component (solvent with a boiling point of 130 to 510°C) in the aluminum paste of conventional gravure printing inks with a solvent that has a relatively lower boiling point, thereby reducing the amount of high-boiling-point solvent component. In addition, it provides coated materials with good adhesion and brightness to the substrate layer of the organic solvent-type gravure ink composition, as well as laminates with excellent laminate strength and retort resistance. [Solution] A coated object having an ink layer with a thickness of 0.3 to 5 μm made of an organic solvent-type gravure ink composition on at least one surface of a substrate layer, wherein the organic solvent-type gravure ink composition comprises an aluminum pigment that satisfies all specific conditions, solvent A, solvent B, solvent C, and a grinding aid, wherein solvent A is a solvent with a boiling point of 130 to 510°C, and solvent B is a solvent with a relatively lower boiling point than solvent A, and includes n-propyl acetate, ethyl acetate, methyl ethyl ketone, isopropyl alcohol, n-propyl alcohol, and propropyl alcohol. A coated article characterized in that, at least one is selected from pyrene glycol monomethyl ether, solvent C is an organic solvent for gravure inks, the grinding aid is at least one selected from oleic acid and stearic acid, and when the total organic solvent-type gravure ink composition is 100% by mass, the aluminum pigment is 3 to 50% by mass, solvent A is 0.01 to 0.5% by mass, the grinding aid is 0.01 to 0.3% by mass, and the total of solvent B and solvent C is 45 to 90% by mass.

Description

Technical Field

[0001] The present invention relates to a coated article, a laminate, a packaging material using the same, and an organic solvent-based gravure ink composition used therefor, and particularly relates to the provision of an organic solvent-based gravure ink composition with a reduced high-boiling solvent component.

Background Art

[0002] Conventionally, metallic pigments typified by metal powders such as aluminum, copper, nickel, and titanium having a flat shape (also referred to as a scale shape) and metal oxide particles such as mica have been mainly used for the purpose of imparting a metallic finish. In particular, an aluminum paste obtained by mixing an aluminum pigment with a solvent having a boiling point of 130 to 510 °C (high-boiling solvent component) such as mineral spirit has many advantages such as productivity, prevention of oxidation during transportation and storage, safety, and ease of formulation as printing ink. However, an ink composition using such an aluminum paste contains a solvent having a boiling point of 130 to 510 °C (high-boiling solvent component), which has a drawback of affecting the adhesion of the ink (for example, Table 1 of JP 2009-227798). In addition, laws such as the French circular economy law have been enacted for the purpose of reducing waste and promoting recycling and reducing risks to the human body. As part of this law, mineral oil (mineral oil) used in packaging materials and printed matter is being regulated because it may interfere with the recycling process or have a harmful effect on health. In particular, solvents having a boiling point of 130 to 510 °C (high-boiling solvent component) such as mineral oil aromatic hydrocarbons (MOAH) and mineral oil saturated hydrocarbons (MOSH) are regarded as problems, and the demand for gravure ink compositions that do not contain such solvents is increasing.

[0003] As a method for improving adhesion, Patent Documents 2 to 4 propose an ink composition using a resin-attached aluminum pigment by attaching a resin to an aluminum pigment. However, the aluminum pigment is used in a paste form and still contains a high concentration of mineral spirit.

[0004] For example, Patent Document 5 describes a method for replacing a high-boiling point solvent in aluminum paste with a low-boiling point solvent. However, this invention relates to a method for manufacturing a transfer sheet, and the transfer sheet is created by forming a release varnish, metallic ink, and adhesive varnish in that order on a base sheet, but there is no description or suggestion regarding the adhesion between the base sheet and the metallic ink. Furthermore, there is no description or suggestion regarding its use as a packaging bag.

[0005] Furthermore, Patent Document 6 proposes a packaging bag equipped with a glossy printed layer, and uses aluminum paste for the glossy printed layer. However, since the aluminum paste is thought to contain a considerable amount of mineral spirits, there is a risk that the adhesion will be poor. In addition, it is not a packaging bag with retort resistance, and there is no description or suggestion of using it for that purpose, so there is a risk that the retort resistance will be poor. The examples also do not describe or suggest any evaluation of adhesion or retort resistance.

[0006] Furthermore, Patent Document 7 proposes an organic compound that is liquid at room temperature and has a thermal decomposition initiation temperature of 200°C or higher, and an aluminum pigment containing 2% or less of volatile compounds. A volatile organic compound with a boiling point of 50°C or higher and 260°C or lower is used as a solvent during the pulverization of the aluminum pigment, and this is removed in a later process to reduce the concentration to 2% or less. However, the evaluation was based on a resin composition obtained by mixing the aluminum pigment with a resin and then injection-molding the resulting molded product. There is no description or suggestion regarding its use as a printing ink, nor is there any description or suggestion regarding the packaging bag. If it were used as a printing ink, temperatures above 200°C would be extremely rare, so organic compounds with a thermal decomposition initiation temperature of 200°C or higher would remain in the ink coating, potentially resulting in poor adhesion and retort resistance.

[0007] Furthermore, Patent Document 8 proposes an aluminum pigment composition containing a polyol compound having two or more hydroxyl groups of a specific number-average molecular weight, with a volatile organic solvent having a boiling point of 260°C or lower, containing 2% or less, and states that it can be used as a printing ink. However, there is no mention of printing on a film substrate, nor is there any description or suggestion of evaluations regarding adhesion or retort resistance.

[0008] Furthermore, Patent Document 9 proposes a gravure ink composition for forming a microwave heating layer, comprising a vapor-deposited aluminum pigment, an organic solvent, and a fatty acid which is a monocarboxylic acid having 8 to 22 carbon atoms, wherein the fatty acid content in the microwave heating layer formation gravure ink composition is 0.01 to 5% by mass, and the aspect ratio of the vapor-deposited aluminum pigment is 100 to 3000. This gravure ink composition is said to have excellent laminate strength and retort resistance. However, the characteristic feature is that by using a vapor-deposited aluminum pigment, it reacts with microwave irradiation, generates heat, and forms an evaporation mechanism. This evaporation mechanism does not occur with raw material aluminum powder produced by the atomization method or with resin-coated aluminum pigments. Moreover, it is clear that these gravure ink compositions containing aluminum pigments contain a considerable amount of mineral spirits, and there is no description or suggestion regarding reducing the content of these mineral spirits.

[0009] Furthermore, Patent Document 10 describes a high-brightness printed material in which a high-brightness gravure ink composition forms a high-brightness printed layer on at least one surface of a plastic substrate film with an ink layer having a thickness of 0.1 to 3 μm, wherein the high-brightness gravure ink composition comprises an untreated vapor-deposited aluminum pigment having an average thickness of 50 nm or less and a thermoplastic resin, wherein the thermoplastic resin comprises a carboxyl group-modified vinyl chloride / vinyl acetate copolymer resin (b1) having an acid value of 2 mg KOH / g or more and a polyurethane resin (b2), and the carboxyl group A high-brightness printed material has been proposed in which the modified vinyl chloride / vinyl acetate copolymer resin (b1) and the polyurethane resin (b2) have a solid content weight ratio of (b1) / (b2) = 100 / 0 to 5 / 95, and the untreated vapor-deposited aluminum pigment (A) and the thermoplastic resin (B) have a solid content weight ratio of (A) / (B) = 90 / 10 to 10 / 90, and is said to have excellent laminate strength. However, the high brightness of the printed material is characterized by the use of vapor-deposited aluminum pigment, and this high brightness is not achieved with resin-coated aluminum pigment. Furthermore, it is clear that the gravure ink composition containing this aluminum pigment contains a considerable amount of mineral spirits, and there is no description or suggestion regarding the reduction of this mineral spirit content.

[0010] Furthermore, Patent Document 11 describes a microwave-safe printed material in which a gravure ink composition for microwave ovens forms a microwave-safe printed layer on at least one surface of a plastic substrate film with an ink layer having a thickness of 0.1 to 3 μm, wherein the gravure ink composition for microwave ovens comprises an aluminum pigment obtained by atomization and not subjected to polymerization treatment, and a thermoplastic resin, wherein the thermoplastic resin comprises an acid-modified vinyl chloride / vinyl acetate copolymer resin and a polyurethane resin, the solid content weight ratio of the acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) to the polyurethane resin (b2) is (b1) / (b2) = 5 / 95 to 95 / 5, and the acid-modified vinyl chloride / vinyl acetate copolymer resin (b1) is acid A microwave-safe printed material has been proposed in which a carboxyl group-modified vinyl chloride / vinyl acetate copolymer resin with a KOH value of 3 to 30 mg / g is used, and the solid weight ratio of the unpolymerized aluminum pigment (A) to the thermoplastic resin (B) is (A) / (B) = 60 / 40 to 1 / 99, and it is said to have excellent laminate strength. However, the aluminum paste containing the unpolymerized aluminum pigment obtained by the atomization method is estimated to contain about 30% mineral spirits, and when this is used as a gravure ink composition for microwave ovens, the mineral spirit content is estimated to be about 1.5%, and there is no description or suggestion for further reducing the mineral spirit content. In addition, Comparative Example 5 of Patent Document 11 discloses a gravure ink composition for microwave ovens containing about 0.06% mineral spirits, but it is clear that the aluminum pigment content is too low, resulting in insufficient brightness, and the problem of achieving high brightness cannot be solved.

[0011] Furthermore, Patent Document 12 proposes a high-brightness laminate ink composition for retort resistance in which a resin-coated aluminum paste obtained by coating aluminum fine powder with a particle size of 5 to 20 μm with an acrylic resin, and a binder resin, wherein the resin-coated aluminum paste makes up 2 to 30% by weight in terms of solid content in the high-brightness ink composition, and is said to have lamination strength and retort resistance. However, a characteristic feature is that a laminate with excellent retort resistance can be obtained by using resin-coated aluminum fine powder, which does not occur with uncoated aluminum fine powder. Furthermore, in order to obtain an acrylic resin-coated aluminum paste, the process involves first polymerizing an unsaturated monomer onto fine aluminum powder in mineral spirits, and then substituting the mineral spirits with propylene glycol monomethyl ether to obtain an acrylic resin-coated aluminum paste. However, the purpose of using propylene glycol monomethyl ether is to remove unreacted monomers and resin that is not adsorbed or fixed to the surface during the acrylic resin coating process, and not to reduce the mineral spirit content. Moreover, there is no description or suggestion regarding the extent to which substitution should be performed.

[0012] Furthermore, Patent Document 13 proposes a packaging material having a base material, a glossy printing layer, an adhesive layer, and a sealant in that order, wherein the glossy printing layer contains a glossy pigment and a urethane resin, the glossy pigment is coated with a higher fatty acid, and the urethane resin has constituent units derived from sebaciate-based polyester polyol, and is said to have heat resistance, acid resistance, and alcohol resistance, as well as improved laminate strength and reduced delamination. The glossy pigment uses an aluminum paste containing aluminum flakes coated with a higher fatty acid, and is thought to contain high-boiling point solvent components such as mineral spirits, but there is no description or suggestion regarding the content of these mineral spirits, nor is there any description or suggestion regarding reducing them. Also, there is no description or suggestion regarding the content of higher fatty acids.

[0013] Furthermore, Patent Document 14) proposes a high-brightness printing ink containing a polyester polyol-type urethane resin with a molecular weight of 10,000 to 20,000 and a polyester polyol-type urethane resin with a molecular weight of 70,000 to 80,000, a softening point of 40 to 50°C and a hydroxyl value of 1 to 10, and further containing 1 to 40% of pulverized metal film fragments obtained by crushing a metal film. This ink yields a high-brightness printing ink, and while organic fatty acids such as stearic acid and oleic acid, and cellulose derivatives such as nitrocellulose are listed as surface treatment agents for treating the surface of the metal film fragments, only nitrocellulose is described in the examples. Although an aluminum thin film fragment slurry is prepared, there is no description or suggestion of including high-boiling point solvent components such as mineral spirits, nor is there any description or suggestion of reducing them.

[0014] Furthermore, Patent Document 15 proposes a high-brightness gravure ink in which metal fragments obtained by crushing a vapor-deposited metal film are dispersed in a resin varnish, and a high-brightness gravure ink can be obtained. Organic fatty acids such as stearic acid and oleic acid are mentioned to coat the surface of the vapor-deposited aluminum fragments, and examples are disclosed in which vapor-deposited aluminum fragments, toluene, oleic acid, or stearic acid are blended, but there is no description or suggestion of the inclusion of high-boiling point solvent components such as mineral spirits, nor is there any description or suggestion of reducing them. Also, as a comparative example, a gravure ink using aluminum paste is disclosed, and it is thought to contain high-boiling point solvent components such as mineral spirits, but there is no description or suggestion of the mineral spirit content, nor is there any description or suggestion of reducing it. [Prior art documents] [Patent Documents]

[0015] [Patent Document 1] Japanese Patent Publication No. 2009-227798 [Patent Document 2] Japanese Patent Publication No. 2017-057309 [Patent Document 3] Japanese Patent Publication No. 2019-189705 [Patent Document 4] Japanese Patent Application Laid-Open No. 2019-189801 [Patent Document 5] Japanese Patent Application Laid-Open No. 59-129189 [Patent Document 6] Japanese Patent Application Laid-Open No. 2021-160802 [Patent Document 7] Japanese Patent Application Laid-Open No. 2015-074711 [Patent Document 8] Japanese Patent Application Laid-Open No. 2019-183088 [Patent Document 9] Japanese Patent No. 7406034 [Patent Document 10] Japanese Patent No. 6894559 [Patent Document 11] Japanese Patent No. 6935564 [Patent Document 12] Japanese Patent Application Laid-Open No. 2010-053193 [[ID=​​​​​​​​​​​​​​​​​​​​​​​​​​​The present inventors have provided a coating having an ink layer with a thickness of 0.3 to 5 μm on at least one surface of a substrate layer, wherein the organic solvent-type gravure ink composition comprises an aluminum pigment satisfying all specific conditions, solvent A, solvent B, solvent C, and a grinding aid, wherein solvent A is a solvent with a boiling point of 130 to 510°C, and solvent B is a solvent with a relatively lower boiling point than solvent A, and includes n-propyl acetate, ethyl acetate, methyl ethyl ketone, isopropyl alcohol, n-propyl alcohol, and propylene glycol monomethyl alcohol. The present invention was completed by finding that the above problem can be solved by a coating characterized in that the solvent C is an organic solvent for gravure inks, the pulverizing aid is at least one selected from oleic acid and stearic acid, and when the total amount of the organic solvent-type gravure ink composition is 100% by mass, the aluminum pigment is 3 to 50% by mass, the solvent A is 0.01 to 0.5% by mass, the pulverizing aid is 0.01 to 0.3% by mass, and the total amount of solvent B and solvent C is 45 to 90% by mass.

[0018] In other words, the present invention is (1) A coated product having an ink layer with a thickness of 0.3 to 5 μm made of an organic solvent-type gravure ink composition on at least one surface of a substrate layer, The aforementioned organic solvent-type gravure ink composition comprises an aluminum pigment satisfying all of the following (a) to (d), solvent A, solvent B, solvent C, and a grinding aid. The solvent A is a solvent with a boiling point of 130 to 510°C. The solvent B is a solvent with a relatively lower boiling point than the solvent A, and is at least one selected from n-propyl acetate, ethyl acetate, methyl ethyl ketone, isopropyl alcohol, n-propyl alcohol, and propylene glycol monomethyl ether. The solvent C is an organic solvent for gravure inks, The aforementioned grinding aid is at least one selected from oleic acid and stearic acid. Furthermore, when the total amount of the organic solvent-type gravure ink composition is 100% by mass, The aluminum pigment is present in an amount of 3 to 50% by mass. The solvent A is 0.01 to 0.5% by mass, The aforementioned grinding aid is 0.01 to 0.3% by mass, A coated article characterized in that the total amount of solvent B and solvent C is 45 to 90% by mass. (a) The raw material aluminum powder is atomized powder. (b) Not coated with resin. (c) The average thickness is 0.1 to 2 μm. (d) The aspect ratio must be between 2.5 and 200. (2) A laminate having an ink layer with a thickness of 0.3 to 5 μm made of an organic solvent-type gravure ink composition on at least one surface of a substrate layer, and a sealant layer or a sealing layer on the ink layer, The aforementioned organic solvent-type gravure ink composition comprises an aluminum pigment satisfying all of the following (a) to (d), solvent A, solvent B, solvent C, and a grinding aid. The solvent A is a solvent with a boiling point of 130 to 510°C. The solvent B is a solvent with a relatively lower boiling point than the solvent A, and is at least one selected from n-propyl acetate, ethyl acetate, methyl ethyl ketone, isopropyl alcohol, n-propyl alcohol, and propylene glycol monomethyl ether. The solvent C is an organic solvent for gravure inks, The aforementioned grinding aid is at least one selected from oleic acid and stearic acid. Furthermore, when the total amount of the organic solvent-type gravure ink composition is 100% by mass, The aluminum pigment is present in an amount of 3 to 50% by mass. The solvent A is 0.01 to 0.5% by mass, The aforementioned grinding aid is 0.01 to 0.3% by mass, A laminate characterized in that the total amount of solvent B and solvent C is 45 to 90% by mass. (a) The raw material aluminum powder is atomized powder. (b) Not coated with resin. (c) The average thickness is 0.1 to 2 μm. (d) The aspect ratio must be between 2.5 and 200. (3) A step of preparing the substrate layer, A method for manufacturing a coated product, comprising a gravure printing step of printing an ink layer made of an organic solvent-type gravure ink composition to at least one of the substrate layers with a film thickness of 0.3 to 5 μm, The aforementioned organic solvent-type gravure ink composition comprises an aluminum pigment satisfying all of the following (a) to (d), solvent A, solvent B, solvent C, and a grinding aid. The solvent A is a solvent with a boiling point of 130 to 510°C. The solvent B is a solvent with a relatively lower boiling point than the solvent A, and is at least one selected from n-propyl acetate, ethyl acetate, methyl ethyl ketone, isopropyl alcohol, n-propyl alcohol, and propylene glycol monomethyl ether. The solvent C is an organic solvent for gravure inks, The aforementioned grinding aid is at least one selected from oleic acid and stearic acid. Furthermore, when the total amount of the organic solvent-type gravure ink composition is 100% by mass, The aluminum pigment is present in an amount of 3 to 50% by mass. The solvent A is 0.01 to 0.5% by mass, The aforementioned grinding aid is 0.01 to 0.3% by mass, A method for manufacturing a coated product, characterized in that the total amount of solvent B and solvent C is 45 to 90% by mass. (a) The raw material aluminum powder is atomized powder. (b) Not coated with resin. (c) The average thickness is 0.1 to 2 μm. (d) The aspect ratio must be between 2.5 and 200. (4) A step of preparing the substrate layer, A gravure printing process in which an ink layer made of an organic solvent-type gravure ink composition is printed on at least one of the substrate layers to a thickness of 0.3 to 5 μm, A method for manufacturing a laminate, comprising a lamination step to create a sealant layer on the ink layer or a coating step to create a seal layer, The aforementioned organic solvent-type gravure ink composition comprises an aluminum pigment satisfying all of the following (a) to (d), solvent A, solvent B, solvent C, and a grinding aid. The solvent A is a solvent with a boiling point of 130 to 510°C. The solvent B is a solvent with a relatively lower boiling point than the solvent A, and is at least one selected from n-propyl acetate, ethyl acetate, methyl ethyl ketone, isopropyl alcohol, n-propyl alcohol, and propylene glycol monomethyl ether. The solvent C is an organic solvent for gravure inks, The aforementioned grinding aid is at least one selected from oleic acid and stearic acid. Furthermore, when the total amount of the organic solvent-type gravure ink composition is 100% by mass, The aluminum pigment is present in an amount of 3 to 50% by mass. The solvent A is 0.01 to 0.5% by mass, The aforementioned grinding aid is 0.01 to 0.3% by mass, A method for producing a laminate, characterized in that the total amount of solvent B and solvent C is 45 to 90% by mass. (a) The raw material aluminum powder is atomized powder. (b) Not coated with resin. (c) The average thickness is 0.1 to 2 μm. (d) The aspect ratio must be between 2.5 and 200. (5) A label characterized by being made using the coating described in (1), (6)(2) A packaging body characterized by being made using the laminate described above, (7) In an organic solvent-type gravure ink composition for use in a coated product having an ink layer with a thickness of 0.3 to 5 μm on at least one surface of a substrate layer, The aforementioned organic solvent-type gravure ink composition comprises an aluminum pigment satisfying all of the following (a) to (d), solvent A, solvent B, solvent C, and a grinding aid. The solvent A is a solvent with a boiling point of 130 to 510°C. The solvent B is a solvent with a relatively lower boiling point than the solvent A, and is at least one selected from n-propyl acetate, ethyl acetate, methyl ethyl ketone, isopropyl alcohol, n-propyl alcohol, and propylene glycol monomethyl ether. The solvent C is an organic solvent for gravure inks, The aforementioned grinding aid is at least one selected from oleic acid and stearic acid. Furthermore, when the total amount of the organic solvent-type gravure ink composition is 100% by mass, The aluminum pigment is present in an amount of 3 to 50% by mass. The solvent A is 0.01 to 0.5% by mass, The aforementioned grinding aid is 0.01 to 0.3% by mass, An organic solvent-type gravure ink composition characterized in that the total amount of solvent B and solvent C is 45 to 90% by mass. (a) The raw material aluminum powder is atomized powder. (b) Not coated with resin. (c) The average thickness is 0.1 to 2 μm. (d) The aspect ratio must be between 2.5 and 200. (8) In an organic solvent-type gravure ink composition for use in a laminate having an ink layer with a thickness of 0.3 to 5 μm on at least one surface of a substrate layer, and a sealant layer on the ink layer, The aforementioned organic solvent-type gravure ink composition comprises an aluminum pigment satisfying all of the following (a) to (d), solvent A, solvent B, solvent C, and a grinding aid. The solvent A is a solvent with a boiling point of 130 to 510°C. The solvent B is a solvent with a relatively lower boiling point than the solvent A, and is at least one selected from n-propyl acetate, ethyl acetate, methyl ethyl ketone, isopropyl alcohol, n-propyl alcohol, and propylene glycol monomethyl ether. The solvent C is an organic solvent for gravure inks, The aforementioned grinding aid is at least one selected from oleic acid and stearic acid. Furthermore, when the total amount of the organic solvent-type gravure ink composition is 100% by mass, The aluminum pigment is present in an amount of 3 to 50% by mass. The solvent A is 0.01 to 0.5% by mass, The aforementioned grinding aid is 0.01 to 0.3% by mass, An organic solvent-type gravure ink composition characterized in that the total amount of solvent B and solvent C is 45 to 90% by mass. (a) The raw material aluminum powder must be atomized powder. (b) Not coated with resin. (c) The average thickness is 0.1 to 2 μm. (d) The aspect ratio must be between 2.5 and 200. This concerns... [Effects of the Invention]

[0019] According to the present invention, by replacing the high-boiling-point solvent component (solvent with a boiling point of 130 to 510°C) in the aluminum paste of conventional gravure printing inks with a solvent that has a relatively lower boiling point than the high-boiling-point solvent component, the environmental burden is reduced, and in addition, it is possible to provide coated products with good adhesion and brightness to the substrate of the organic solvent-type gravure ink composition, as well as laminates with excellent laminate strength and retort resistance. [Modes for carrying out the invention]

[0020] 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.

[0021] The organic solvent-type gravure ink composition of the present invention preferably contains an aluminum pigment that satisfies all of the following (a) to (d), solvent A, solvent B, solvent C, and a grinding aid.

[0022] Solvent A refers to solvent components with a boiling point of 130 to 510°C (hereinafter also referred to as high-boiling-point solvent components). High-boiling-point solvent components, in particular, include mineral oil components such as mineral oil aromatic hydrocarbons (MOAH) and mineral oil saturated hydrocarbons (MOSH) (mineral spirits and solvent naphtha are said to contain such mineral oil components), many of which fall within the aforementioned boiling point range as mixtures. These are components that have been conventionally used when making a paste from aluminum pigments (hereinafter referred to as aluminum paste), and examples include industrial gasoline such as mineral spirits and solvent naphtha (including those called medium-boiling-point aromatic naphtha), hydrocarbon solvents such as xylene, tetralin, and decalin, isoparaffinic hydrocarbon solvents such as 2,2,4,6,6-pentamethylheptane, and mineral oils. These can be used individually or in mixtures of two types. The most commonly used are mineral spirits and solvent naphtha.

[0023] The solvent B is a solvent with a relatively lower boiling point than solvent A, and is preferably at least one selected from n-propyl acetate, ethyl acetate, methyl ethyl ketone, isopropyl alcohol, n-propyl alcohol, and propylene glycol monomethyl ether. These can be used individually or in combination of two types.

[0024] The solvent C is an organic solvent for gravure inks, and is an example of an aromatic hydrocarbon solvent such as toluene or xylene; an aliphatic hydrocarbon solvent such as hexane, cyclohexane, methylcyclohexane, or ethylcyclohexane; an alcohol solvent such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, 1-butanol, 2-butanol, isobutanol, or tert-butanol; an ester solvent such as ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, or tert-butyl acetate; a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone; or an ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, or ethylene glycol dimethyl ether. Examples of glycol ether solvents include ethyl 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-formed products 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.

[0025] The aforementioned grinding aid is preferably used when preparing aluminum paste. The grinding aid is not particularly limited, but examples include saturated fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid; unsaturated fatty acids such as oleic acid, linoleic acid, α-linolenic acid, and arachidonic acid; aliphatic amines such as stearylamine; aliphatic alcohols such as stearyl alcohol and oleyl alcohol; and aliphatic amides such as stearic acid amide and oleic acid amide. Among these, it is more preferable that at least one selected from stearic acid and oleic acid is used. If a non-leafing type is desired, it is preferable to use oleic acid, and if a leafing type is desired, it is preferable to use stearic acid. The organic solvent-type gravure ink composition of the present invention is more preferably a non-leafing type.

[0026] A typical method for producing aluminum paste involves using a conventionally known method to load aluminum pigment, solvent A (high-boiling point solvent component), and grinding aid into a grinder such as a ball mill, grinding them to obtain an aluminum slurry, sieving it, removing excess solvent A (high-boiling point solvent component) with a filter press or the like to obtain a cake with a heating residue of about 90% by mass, then transferring it to a vertical mixer or the like, adding solvent A (high-boiling point solvent component), mixing and stirring to obtain a uniform aluminum paste containing about 70% by mass of heating residue (solid content), about 30% by mass of solvent A (high-boiling point solvent component), and about 0.05 to 2% by mass of grinding aid.

[0027] In the present invention, in the method for producing the aluminum paste described below, after obtaining a cake with a heating residue of about 90% by mass using the aluminum pigment described later, the cake is transferred to a vertical mixer or the like, solvent B is added instead of solvent A (high-boiling point solvent component), and after mixing and stirring, excess solvent A (high-boiling point solvent component) is removed using a filter press or the like. This process is repeated to increase the content of solvent B, and an aluminum paste is obtained in which the heating residue (solid content) is about 70-90% by mass, solvent B is about 10-30% by mass, and solvent A (high-boiling point solvent component) is about 1% by mass or less. As a result, it is possible to significantly reduce solvent A (high-boiling point solvent component) compared to the general aluminum paste, and it is possible to take into consideration the regulations based on the French Circular Economy Law (contributing to the reduction of environmental impact) and to form coated products that comply with these regulations. Furthermore, within the range applicable to aluminum paste, it is possible to obtain aluminum paste with adjusted heating residue (solid content) and solvent B content.

[0028] The aluminum pigment is preferably one of conventionally known types, but it is more preferable that the raw material aluminum powder is atomized powder produced by the atomization method. The pulverizing aid is used to pulverize the atomized powder, but no further processing is required, and resin coating of the atomized powder is not necessary. The aluminum pigment obtained by the aforementioned grinding process has an average thickness of 0.1 to 2 μm, an average particle size of 5 to 20 μm, and a specific surface area of ​​1 to 30 m². 2The particles are thin and flaky, weighing approximately 1 / g. The average thickness can be calculated by taking the average thickness of a randomly selected region for a single particle, and then taking the average thickness of multiple particles (e.g., 10 or more) from that average, with a more preferable value of 0.15 to 1 μm. The average particle diameter can be calculated as the volume-based median diameter D50 from the volume-based cumulative particle size distribution measured by a laser diffraction particle size distribution analyzer, with a more preferable value of 5 to 15 μm, and even more preferable of 5 to 10 μm. In this specification, average particle diameter and average length are considered synonymous. The specific surface area can be measured, for example, by the BET method, which is a method of measuring the specific surface area of ​​a solid particle by adsorbing gas molecules (usually nitrogen gas) onto the solid particle and measuring the amount of adsorbed gas molecules. The specific surface area can be measured using various BET measuring devices.

[0029] The ratio of the average length to the average thickness [average length / average thickness] can be defined as the aspect ratio, and the aspect ratio of the resulting aluminum pigment is preferably 2.5 to 200, more preferably 5 to 150, and even more preferably 10 to 100.

[0030] In other words, the aluminum pigment of the present invention achieves excellent adhesion and brightness by satisfying all of the following specific conditions: (a) the raw material aluminum powder is atomized powder, (b) it is not coated with resin, (c) the average thickness is 0.1 to 2 μm, and (d) the aspect ratio is 2.5 to 200.

[0031] When the total amount of the organic solvent-type gravure ink composition is 100% by mass, the amount of aluminum pigment is preferably 3 to 50% by mass. It is more preferably 45% by mass or less, and even more preferably 40% by mass or less. It is also more preferably 5% by mass or more, and even more preferably 10% by mass or more.

[0032] When the total volume of the organic solvent-type gravure ink composition is 100% by mass, the solvent A is preferably 0.01 to 0.5% by mass. More preferably 0.4% by mass or less, even more preferably 0.3% by mass or less, and even more preferably 0.2% by mass or less. Furthermore, it is more preferably 0.02% by mass or more, even more preferably 0.03% by mass or more, even more preferably 0.04% by mass or more, and even more preferably 0.05% by mass or more. By having the solvent A content within the above range, it is possible to form a coated product with improved adhesion of the organic solvent-type gravure ink composition to the substrate layer, and to form a laminate with excellent lamination strength and retort resistance.

[0033] When the total amount of the organic solvent-type gravure ink composition is 100% by mass, the amount of the pulverizing aid is preferably 0.01 to 0.3% by mass. If it is lower than 0.01% by mass, the aluminum pigment tends to aggregate, and if it exceeds 0.3% by mass, the laminate strength decreases. In preparing the aluminum paste, it is preferable to use 0.05 to 10 parts of the pulverizing aid per 100 parts of atomized powder, more preferably 0.1 to 5 parts, and even more preferably 0.2 to 2 parts. If the amount is less than 0.05 parts, the resulting aluminum pigment is prone to aggregation, and if it exceeds 10 parts, it may reduce the strength of the coating film.

[0034] When the total amount of the organic solvent-type gravure ink composition is 100% by mass, the sum of solvent B and solvent C is preferably 45 to 90% by mass, more preferably 50 to 80% by mass, and even more preferably 60 to 70% by mass. If it is less than 45% by mass, sufficient printability cannot be obtained, the fluidity will be poor, and the suitability for ink manufacturing will be inferior. If it is more than 90% by mass, the adhesion to the substrate layer will decrease, the ink film thickness will become locally uneven, irregular shades of gray (swimming phenomenon) may occur on the printed surface, the viscosity will be low, and the pigment may be prone to settling. Solvent B is a solvent with a relatively lower boiling point than solvent A, and as described above, in the method for producing the aluminum paste according to the present invention, it is a solvent used for substitution in order to reduce solvent A (high-boiling point solvent component) to about 1% or less, and is contained in the aluminum paste at a concentration of about 30% by mass. It may be different from or the same as the organic solvent for gravure ink of solvent C.

[0035] The organic solvent-based gravure ink composition of the present invention may also contain resins, 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 ink composition.

[0036] The aforementioned resins include shellacs, rosins, rosin-modified maleic acid resins, rosin-modified phenolic resins, nitrated cotton, cellulose acetate, vinyl chloride / vinyl acetate copolymer resins, polyurethane resins, cellulose acetylpropionate, cellulose acetyl butyrate, chlorinated rubber, cyclic rubber, polyethylene resins, polypropylene resins, vinyl chloride resins, polyamide resins, ethylene-(meth)acrylic acid copolymers, polyester resins, polyvinylidene chloride resins, vinyl acetate resins, ketone resins, butyral resins, chlorinated polypropylene resins, chlorinated polyethylene resins, chlorinated ethylene vinyl acetate resins, ethylene vinyl acetate resins, (meth)acrylic resins, and s Preferred resins include ethylene 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, polyetherketone resin, modified polyphenylene ether resin, polyphenylene sulfone resin, polyimide resin, polyamideimide resin, amorphous polyarylate resin, polyetheretherketone resin, acrylic emulsion, urethane emulsion, polyvinyl alcohol resin, ethylene-vinyl alcohol resin, and polylactic acid. Among these, nitrated cotton, polyurethane resin, polyamide resin, (meth)acrylic resin, chlorinated polypropylene resin, chlorinated polyethylene resin, and vinyl chloride / vinyl acetate copolymer resin are more preferred. These resins may be one type or two or more types.

[0037] The resin is preferably 2 to 55% by mass, more preferably 5 to 45% by mass, and even more preferably 10 to 35% by mass, when the total organic solvent-type gravure ink composition is considered to be 100% by mass, as solid content. If it is less than 2% by mass, the amount applied during printing will be insufficient, and if it is more than 55% by mass, the fluidity will be poor, making it difficult to form an ink.

[0038] The aforementioned colorant 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. Furthermore, the organic solvent-type gravure ink composition of the present invention may be mixed with the colorants described later to form a gravure printing ink.

[0039] In addition to solvents A, B, and C, the organic solvent-type gravure ink composition of the present invention may also contain, to the extent that it does not impair the properties of the ink composition, intermediate boiling point naphtha or isoparaffinic hydrocarbon compounds having a boiling point range of about 80 to 130°C.

[0040] The organic solvent-based gravure ink composition of the present invention can be manufactured by known methods by uniformly dissolving or dispersing an aluminum paste containing an aluminum pigment that satisfies all specific conditions, solvent A, solvent B, and a grinding aid, an organic solvent for gravure ink which is solvent C, a resin, a colorant, various additives, etc. Dissolution or dispersion can be carried out using various agitators 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 organic solvent-type gravure 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.

[0041] The viscosity of the organic solvent-type gravure ink composition is not particularly limited, as long as it does not interfere with printing. Considering the suitability of the ink 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 pigment 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 into containers. In this case, it can be measured using a commercially available viscometer such as a Brookfield viscometer or a cone-plate viscometer.

[0042] The aforementioned organic solvent-based gravure 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 in 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.

[0043] The aforementioned diluent can be any solvent that can be used to adjust the viscosity of the organic solvent-type gravure ink composition, and commercially available solvents can also be used; there are no particular restrictions. Examples of commercially available solvents include WA735 solvent (alcohol-based solvent), 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.).

[0044] During printing, a curing agent may be added to the organic solvent-based gravure 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.).

[0045] In the coated product of the present invention, an ink layer made of the organic solvent-type gravure ink composition is preferably formed on at least one surface of the substrate layer with a film thickness of 0.3 to 5 μm, more preferably 0.5 to 3 μm, and even more preferably 0.1 to 2 μm. If it is less than 0.3 μm, the brightness may decrease, and if it is greater than 5 μm, the lamination strength will be inferior.

[0046] The substrate layer is preferably at least one selected from paper substrates, plastic films or sheets, 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 to the printed surface, corona treatment, low-temperature plasma treatment, flame treatment, solvent treatment, coating treatment, etc. can be applied, or a pre-treated surface 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 layer is not particularly limited as long as it does not impair printability, winding suitability, etc., but 5 to 300 μm is preferred, and 6 to 250 μm is more preferred. In addition, if the substrate layer is a heat-sealable film such as polyethylene film, the substrate layer 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 laminate of the present invention preferably has a sealant layer or a sealing layer on the ink layer of the coated material.

[0049] The sealant layer may be, for example, a laminate with heat-sealing properties, a known sealant film bonded together, or a resin coating by an extrusion lamination method, while the seal layer may be a layer formed by, for example, coating with a heat sealant or a hot melt agent.

[0050] As long as sufficient sealing strength can be ensured, the bonding method for the sealant layer can be appropriately selected according to the base layer, application, and composition. For example, bonding of a known sealant film to the ink layer on the base layer 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.

[0051] Examples of the sealant film include polyolefin films such as polyethylene, polypropylene, ethylene-vinyl acetate, and copolymers thereof, as well as their co-extruded films and colored films, 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. Alternatively, commercially available easy-peel films may also be used.

[0052] 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, dip coaters, etc., 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.

[0053] 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.

[0054] 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 base layer, application, and structure. For example, heat sealing agents or hot melt coatings are 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 preferable to have a thickness of 1 to 50 μm for hot melt adhesive coatings and 0.01 to 30 μm for heat sealing agent coatings. Adhesive coatings or other adhesives may also be used.

[0055] Examples of resins used in heat sealing agents 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. Examples include types in which these resins are dissolved in a solvent, or dispersed in water as acrylic emulsions, urethane emulsions, ethylene-vinyl alcohol emulsions, polyethylene emulsions, polypropylene emulsions, and ethylene vinyl acetate emulsions.

[0056] The laminate of the present invention may include a printing layer made of a gravure printing ink (hereinafter also simply referred to as "gravure ink") different from the organic solvent-type gravure ink composition. The printing layer is preferably laminated between the substrate layer and the ink layer or on top of the ink layer. The thickness of the printed 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 0.01 μm, it is difficult to obtain sufficient print density, and if it is greater than 10 μm, it is difficult to form the printed layer and the blocking resistance is poor.

[0057] In addition to the ink layer and printing layer, the laminate of the present invention may also include 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, straight cut properties, and gas adsorption properties. When an intermediate layer is provided, it is not necessarily required to apply the ink layer to the base layer; the ink layer may be provided in the intermediate layer. However, when imparting gas adsorption properties, it is preferable that the gas barrier layer for imparting gas barrier properties is not placed on the side of the gas adsorption material source that is less likely to be gas adsorbed than the gas adsorption material layer.

[0058] 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 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; polylactic acid films; and gas-adsorbing films with a gas adsorption layer on these films. These may be stretched or unstretched, and one or more types may be laminated. An appropriate one 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 treatments. Treatment of both sides is preferred. The intermediate layer can be any thickness that does not impair printability or winding suitability, preferably 5 to 300 μm, and more preferably 6 to 250 μm.

[0059] The laminate of the present invention can be configured, for example, as follows: substrate layer / printed layer / ink layer, substrate layer / ink layer / printed layer, substrate layer / ink layer / nylon film / sealant layer, substrate layer / ink layer / nylon film / seal layer, or substrate layer / ink layer / printed layer / nylon film / sealant layer. Adhesive layers may also be laminated between each layer.

[0060] The printed layer is a layer coated with a gravure printing ink different from the organic solvent-type gravure ink composition, and preferably contains a resin commonly used in gravure printing inks. Examples of resins used in the gravure printing ink 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. Resins similar to those used in the organic solvent-type gravure ink composition of the present invention can also be used.

[0061] The resin used in the gravure printing ink preferably has 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 solid 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.

[0062] The aforementioned gravure ink may also contain, in addition to the resin used in gravure printing inks, colorants, ink 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.

[0063] The colorant contained in the gravure ink may be the same as the colorant contained in the organic solvent-type gravure ink composition.

[0064] The aforementioned solvent for the ink is used to provide appropriate fluidity and adjust viscosity during the formation of the printed layer, and preferably dissolves or disperses the resin used in the gravure printing ink.

[0065] Examples of solvents for the ink 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, and ethylene glycol dimethyl 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. Preferably, at least one of these is selected, and two or more may be used in combination. Solvents similar to those used in the organic solvent-type gravure ink composition of the present invention can also be used.

[0066] The aforementioned solvent for the ink 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 adhesion to the substrate layer and the ink layer.

[0067] 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.).

[0068] The laminate of the present invention may also have an anchor coat layer, an overcoat layer (also called a protective layer), etc., made of an anchor coat agent or an overcoat agent.

[0069] The thickness of the anchor coat layer is preferably 0.05 to 3 μm, and more preferably 0.1 to 2 μm. If the thickness of the anchor coat layer is less than 0.05 μm, the amount of coating may be insufficient and may not cover the substrate layer, and if it exceeds 3 μm, there is a risk of blocking.

[0070] The thickness of the overcoat layer is preferably 0.05 to 5 μm, and more preferably 0.1 to 3 μm. If the thickness of the overcoat layer is less than 0.05 μm, the protective effect on the ink layer and the printed layer will not be sufficient, and if it exceeds 5 μm, there is a risk of blocking.

[0071] The 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.

[0072] The method for manufacturing a coated product of the present invention preferably includes a step of preparing a substrate layer and a gravure printing step of printing an ink layer made of the organic solvent-type gravure ink composition onto at least one of the substrate layers to a thickness of 0.3 to 5 μm, more preferably a gravure printing step of printing to a thickness of 0.5 to 3 μm, and even more preferably a gravure printing step of printing to a thickness of 0.1 to 2 μm. If the film thickness is less than 0.3 μm, the brightness may decrease, and if the film thickness is greater than 5 μm, the lamination strength is poor. The gravure printing step is more preferably a multi-color gravure printing step using a multi-color gravure printing method.

[0073] The step of preparing the substrate layer is preferably a step of preparing at least one selected from paper substrates, plastic films or sheets, and laminates thereof. Examples of plastic films or sheets and laminates thereof 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. Appropriate materials can be selected considering mechanical strength and dimensional stability. Furthermore, to improve the adhesion of the anchor coat layer to the printed surface, corona treatment, low-temperature plasma treatment, flame treatment, solvent treatment, or coating treatment can be applied, or pre-treated materials 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 layer is not particularly limited as long as it does not impair printability or winding suitability, but 5 to 300 μm is preferred, and 6 to 250 μm is more preferred. Additionally, if the substrate layer is a heat-sealable film such as polyethylene film, the substrate layer itself may function as a sealant layer.

[0074] 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.

[0075] The method for manufacturing the laminate of the present invention preferably includes the steps of: preparing a base layer; printing an ink layer made of the organic solvent-type gravure ink composition onto at least one of the base layers to a thickness of 0.3 to 5 μm; and laminating or coating to create a sealant layer on the ink layer.

[0076] The steps for preparing the substrate layer and the gravure printing step are equivalent to the steps for manufacturing the coated product.

[0077] Preferably, the process includes a lamination step to create a sealant layer on the ink layer or a coating step to create a sealing layer. The lamination process for creating the sealant layer is preferably a lamination process such as bonding a heat-sealable laminate or a known sealant film, or resin coating by an extrusion lamination method. The coating process for creating the sealant layer may include, for example, a coating process such as applying a heat sealant or a hot melt agent.

[0078] The lamination process for creating the sealant layer can be appropriately selected depending on the substrate layer, application, and composition, as long as sufficient sealing strength can be ensured. For example, a process of bonding a known sealant film to an ink layer on the substrate layer via an adhesive (dry lamination, non-solvent lamination, wet lamination), a heat lamination process (thermal lamination), and a resin coating by an extrusion lamination process (extrusion lamination, co-extrusion lamination, PE sandwich lamination) can be preferably used. A laminate can be manufactured by using one or a combination of these processes. There are no particular restrictions on the thickness of the sealant layer produced by the lamination process, but it is preferable to produce a sealant film with a thickness of 2 to 200 μm, and a resin coating by the extrusion lamination method with a thickness of 1 to 100 μm.

[0079] Examples of the sealant film include polyolefin films such as polyethylene, polypropylene, ethylene-vinyl acetate, 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 may be formed by laminating one or more types.

[0080] When using adhesives in the dry lamination process, non-solvent lamination process, wet lamination process, extrusion lamination process, 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. For the adhesive application process to form the sealant layer, known application processes can be used. For example, application processes using coating equipment such as 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.

[0081] Examples of resins that can be used for resin coating by the extrusion lamination process 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.

[0082] The coating process for creating the seal layer can be appropriately selected according to the substrate layer, application, and composition, as long as sufficient seal strength can be ensured. For example, coating processes for heat sealants or hot melts are preferably used. These coating processes can be used individually or in combination to produce the laminate. There are no particular restrictions on the thickness of the seal layer, but it is preferable to have a thickness of 1 to 50 μm for hot melt adhesive coatings and 0.01 to 30 μm for heat sealant coatings. Adhesive coating processes or other adhesives may also be used.

[0083] Examples of resins that can be used in the coating process of the heat sealant 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, cyclic rubber, polyamide resins, vinyl chloride-vinyl acetate copolymers, polyester resins, ketone resins, butyral resins, chlorinated polypropylene resins, chlorinated polyethylene resins, chlorinated ethylene vinyl acetate resins, ethylene vinyl acetate resins, (meth)acrylic resins, urethane resins, ethylene-vinyl alcohol resins, styrene maleic acid resins, casein, and alkyd resins, which may be used 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.

[0084] The method for manufacturing the laminate of the present invention may include a gravure printing step of forming a printed layer made of a gravure printing ink different from the ink layer made of an organic solvent-type gravure ink composition. The gravure printing step of forming the printed layer is preferably a step of forming the printed layer between the substrate layer and the ink layer or on the ink layer. It is preferable to include a gravure printing step in which the printed layer formed by the gravure printing process is printed with a film thickness of 0.01 to 10 μm, more preferably a gravure printing step in which the film thickness is printed with a film thickness of 0.1 to 5 μm, and even more preferably a gravure printing step in which the film thickness is printed with a film thickness of 1 to 3 μm. If the film thickness is less than 0.01 μm, it is difficult to obtain sufficient print density, and if the film thickness is greater than 10 μm, it is difficult to form the printed layer and the blocking resistance is poor.

[0085] The method for manufacturing the laminate of the present invention may include, in addition to the steps of forming the ink layer and the printed layer, 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, straight cut properties, and gas adsorption properties. When the step of forming an intermediate layer is included, it is not necessarily required to be a step of forming an ink layer on the substrate layer, but rather a step of forming an ink layer on the intermediate layer. However, when imparting gas adsorption properties, it is preferable that the gas barrier layer for imparting gas barrier properties is not formed on the side of the gas adsorption material source that is less than the gas adsorption material layer.

[0086] The process of forming the intermediate layer can use 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 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; polylactic acid films; and gas-adsorbent films with a gas adsorption layer on these films. These can 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 treatments. Treatment of both sides is preferred. The intermediate layer to be created can be within a range that does not impair printability or winding suitability, and a thickness of 5 to 300 μm is preferred, with a thickness of 6 to 250 μm being more preferred.

[0087] The present invention's method for manufacturing a laminate can, for example, be used to produce a laminate with the following configurations by combining the above steps: substrate layer / printed layer / ink layer, substrate layer / ink layer / printed layer, substrate layer / ink layer / nylon film / sealant layer, substrate layer / ink layer / nylon film / seal layer, or substrate layer / ink layer / printed layer / nylon film / sealant layer. The method may also include a step of applying an adhesive layer between each layer.

[0088] The gravure printing step for forming the printed layer is a gravure printing step for forming a layer made of a different gravure printing ink than the gravure printing step for forming an ink layer made of the organic solvent-type gravure ink composition, and preferably includes a resin used in ordinary gravure printing inks. Examples of resins used in the gravure printing ink 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 copolymer, polystyrene resin, acrylic resin, acrylic styrene copolymer, polyacrylic acid ester, polyester resin, polyvinylidene chloride resin, ketone resin, polyamide resin, nitrocellulose resin, rosin resin, styrene maleic acid resin, alkyd resin, and ethylene-vinyl alcohol resin. Resins similar to those used in the organic solvent-type gravure ink composition of the present invention can also be used.

[0089] The resin used in the gravure printing ink preferably contains 1 to 70% by mass of solids, more preferably 2 to 65% by mass, and even more preferably 3 to 60% by mass. If the solid 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 the gravure printing process becomes difficult.

[0090] The aforementioned gravure ink may also contain, in addition to the resin used in gravure printing inks, colorants, ink 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.

[0091] The colorant contained in the gravure ink may be the same as the colorant contained in the organic solvent-type gravure ink composition.

[0092] The aforementioned solvent for the ink is used to provide appropriate fluidity and adjust viscosity during the printing layer formation process, and preferably dissolves or disperses the resin used in the gravure printing ink.

[0093] Examples of solvents for the ink 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, and ethylene glycol dimethyl 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. Preferably, at least one of these is selected, and two or more may be used in combination. Solvents similar to those used in the organic solvent-type gravure ink composition of the present invention can also be used.

[0094] The aforementioned solvent for the ink 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 adhesion to the substrate layer and the ink layer.

[0095] The method for manufacturing the laminate of the present invention may include a step of forming an anchor coat layer and an overcoat layer (also called a protective layer) by applying an anchor coat agent and an overcoat agent. The process of forming the anchor coat layer and the overcoat layer (also called a protective layer) is preferably a gravure printing process in which the anchor coat agent and the overcoat agent are gravure printed.

[0096] The thickness of the anchor coat layer formed in the aforementioned anchor coat layer formation step is preferably 0.05 to 3 μm, and more preferably 0.1 to 2 μm. If the thickness of the anchor coat layer is less than 0.05 μm, the amount of coating may be insufficient, and the substrate layer may not be covered. If it exceeds 3 μm, blocking may occur.

[0097] The thickness of the overcoat layer formed in the process described above is preferably 0.05 to 5 μm, and more preferably 0.1 to 3 μm. If the thickness of the overcoat layer is less than 0.05 μm, the protective effect on the ink layer and the printed layer will not be sufficient, and if it exceeds 5 μm, there is a risk of blocking.

[0098] The label of the present invention is preferably made using the aforementioned coating.

[0099] The aforementioned label may be the coated material as is, or it may be made into a label by forming an adhesive layer on the other side of the substrate layer on which the ink layer is formed, and further forming a release layer. The adhesive layer or release layer may be any material that adheres closely to the substrate layer and the release layer, and allows the release layer to be easily peeled off, such as a rubber-based adhesive material or an acrylic resin-based adhesive material. The release layer may be any material such as polyethylene film, polyester film, or paper (release paper). The laminate that forms the label may consist of a base layer / ink layer / printing layer / overcoat layer, a base layer / anchor coat layer / ink layer / printing layer, a base layer / anchor coat layer / ink layer / printing layer / overcoat layer, an adhesive layer / base layer / ink layer / printing layer / overcoat layer, a hot melt layer / base layer / ink layer / printing layer / overcoat layer, an adhesive layer / printing layer / base layer / ink layer / overcoat layer, an adhesive layer / printing layer / base layer / anchor coat layer / ink layer / overcoat layer, and so on.

[0100] The packaging of the present invention is preferably made using the laminated material, and may be used as a packaging bag or lid material.

[0101] The packaging body that becomes the aforementioned packaging bag may be composed of a base layer / ink layer / overcoat layer / sealant layer, a base layer / anchor coat layer / ink layer / overcoat layer / sealant layer, a seal layer / DL / base layer / ink layer / overcoat layer, a seal layer / DL / printed layer / base layer / ink layer / overcoat layer, a seal layer / DL / printed layer / base layer / anchor coat layer / ink layer / overcoat layer, a base layer / printed layer / ink layer / DL / sealant layer, or a base layer / printed layer / ink layer / printed layer / DL / sealant layer. The packaging bag may be any of the well-known forms such as two-side seal, three-side seal, four-side seal, pillow seal, standing pouch, envelope-type seal, gusset, or heat-sealed seal. DL stands for dry laminate.

[0102] The packaging body that serves as the lid material may be composed of a seal layer / DL / base layer / ink layer / overcoat layer, a seal layer / DL / printed layer / base layer / ink layer / overcoat layer, a seal layer / DL / printed layer / base layer / anchor coat layer / ink layer / overcoat layer, a base layer / ink layer / DL / easy peel film (sealant layer), a base layer / ink layer / DL / intermediate layer / easy peel film (sealant layer), a base layer / printed layer / ink layer / DL / easy peel film (sealant layer), a base layer / printed layer / ink layer / printed layer / DL / easy peel film (sealant layer), a base layer / ink layer / DL / hot melt layer, a base layer / ink layer / DL / intermediate layer / hot melt layer, a base layer / printed layer / ink layer / DL / hot melt layer, a base layer / printed layer / ink layer / printed layer / DL / hot melt layer, and so on. The lid material may be any of the well-known forms such as a cover, lid, or cap.

[0103] 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 mass percent.

[0104] [Preparation of aluminum paste] (Manufacturing Example 1) Using 100g of atomized aluminum powder (atomized powder), 2g of oleic acid, and 500mL of solvent naphtha as raw materials, these were placed in a ball mill along with 5kg of 3.2φ bearing balls and ground to obtain a slurry. After grinding was complete, the slurry was sieved through a 37 μm sieve to remove coarse particles, and then excess solvent naphtha was removed by filter pressing to obtain a cake with a heating residue of 90% by mass. The obtained cake was transferred to a vertical mixer, n-propyl acetate was added, and after mixing and stirring for 15 minutes, excess solvent naphtha was removed again by filter pressing. Then, n-propyl acetate was added again in the vertical mixer, and after mixing and stirring, the process of removing solvent naphtha by filter pressing was repeated until the heating residue (aluminum solids) was 70% by mass, thereby obtaining aluminum paste A1. At this time, the content was 29.5% by mass of n-propyl acetate, 0.3% by mass of solvent naphtha, and 0.2% by mass of oleic acid. The aluminum pigment in aluminum paste A1 was of the non-leafing type, with a D50 average particle size of 7 μm, an average thickness of 0.14 μm, and an aspect ratio of 50.

[0105] (Manufacturing example 2) Aluminum paste A2 was obtained in the same manner as aluminum paste A1 in Production Example 1, with a heating residue (aluminum solids) of 90% by mass. At this time, n-propyl acetate was 8.8% by mass, solvent naphtha was 1% by mass, and oleic acid was 0.2% by mass. The aluminum pigment in aluminum paste A2 was of the non-leafing type, with a D50 average particle size of 7 μm, an average thickness of 0.14 μm, and an aspect ratio of 50.

[0106] (Manufacturing Example 3) Using 100g of atomized aluminum powder (atomized powder), 10g of oleic acid, and 500mL of solvent naphtha as raw materials, these were placed in a ball mill along with 5kg of 3.2φ bearing balls and ground to obtain a slurry. After grinding was complete, the slurry was sieved through a 37 μm sieve to remove coarse particles, and then excess solvent naphtha was removed by filter pressing to obtain a cake with a heating residue of 90% by mass. The obtained cake was transferred to a vertical mixer, n-propyl acetate was added, and after mixing and stirring for 15 minutes, excess solvent naphtha was removed again by filter pressing. Then, n-propyl acetate was added again in the vertical mixer, and after mixing and stirring, the process of removing solvent naphtha by filter pressing was repeated until the heating residue (aluminum solids) was 70% by mass, thereby obtaining aluminum paste A3. At this time, the n-propyl acetate content was 28.2% by mass, solvent naphtha was 0.3% by mass, and oleic acid was 1.5% by mass. The aluminum pigment in aluminum paste A3 was of the non-leafing type, with a D50 average particle size of 7 μm, an average thickness of 0.14 μm, and an aspect ratio of 50.

[0107] (Manufacturing example 4) Using 100g of atomized aluminum powder (atomized powder), 0.1g of oleic acid, and 500mL of solvent naphtha as raw materials, these were placed in a ball mill along with 5kg of 3.2φ bearing balls and ground to obtain a slurry. After grinding was complete, the slurry was sieved through a 37 μm sieve to remove coarse particles, and then excess solvent naphtha was removed by filter pressing to obtain a cake with a heating residue of 90% by mass. The obtained cake was transferred to a vertical mixer, n-propyl acetate was added, and after mixing and stirring for 15 minutes, excess solvent naphtha was removed again by filter pressing. Then, n-propyl acetate was added again in the vertical mixer, and after mixing and stirring, the process of removing solvent naphtha by filter pressing was repeated until the heating residue (aluminum solids) was 70% by mass, thereby obtaining aluminum paste A4. At this time, the n-propyl acetate content was 29.65% by mass, solvent naphtha was 0.3% by mass, and oleic acid was 0.05% by mass. The aluminum pigment in aluminum paste A4 was of the non-leafing type, with a D50 average particle size of 7 μm, an average thickness of 0.14 μm, and an aspect ratio of 50.

[0108] (Manufacturing example 5) Using 100g of atomized aluminum powder (atomized powder), 2g of stearic acid, and 500mL of solvent naphtha as raw materials, these were placed in a ball mill along with 5kg of 3.2φ bearing balls and ground to obtain a slurry. After grinding was complete, the slurry was sieved through a 37 μm sieve to remove coarse particles, and then excess solvent naphtha was removed by filter pressing to obtain a cake with a heating residue of 90% by mass. The obtained cake was transferred to a vertical mixer, n-propyl acetate was added, and after mixing and stirring for 15 minutes, excess solvent naphtha was removed again by filter pressing. Then, n-propyl acetate was added again in the vertical mixer, and after mixing and stirring, the process of removing solvent naphtha by filter pressing was repeated until the heating residue (aluminum solids) was 70% by mass, thereby obtaining aluminum paste A5. At this time, the content was 29.5% by mass of n-propyl acetate, 0.3% by mass of solvent naphtha, and 0.2% by mass of stearic acid. The aluminum pigment in aluminum paste A5 was of the leafing type, with an average D50 particle size of 7 μm, an average thickness of 0.14 μm, and an aspect ratio of 50.

[0109] (Manufacturing example 6) Using 100g of atomized aluminum powder (atomized powder), 5g of oleic acid, and 500mL of solvent naphtha as raw materials, these were placed in a ball mill along with 5kg of 3.2φ bearing balls and ground to obtain a slurry. After grinding was complete, the slurry was sieved through a 37 μm sieve to remove coarse particles, and then excess solvent naphtha was removed by filter pressing to obtain a cake with a heating residue of 90% by mass. The obtained cake was transferred to a vertical mixer, n-propyl acetate was added, and after mixing and stirring for 15 minutes, excess solvent naphtha was removed again by filter pressing. Then, n-propyl acetate was added again in the vertical mixer, and after mixing and stirring, the process of removing solvent naphtha by filter pressing was repeated until the heating residue (aluminum solids) was 90% by mass, thereby obtaining aluminum paste A6. At this time, the n-propyl acetate content was 8.7% by mass, solvent naphtha was 0.3% by mass, and oleic acid was 1% by mass. The aluminum pigment in aluminum paste A6 was of the non-leafing type, with a D50 average particle size of 7 μm, an average thickness of 0.14 μm, and an aspect ratio of 50.

[0110] (Manufacturing example 7) Using 100g of atomized aluminum powder (atomized powder), 2g of oleic acid, and 500mL of solvent naphtha as raw materials, these were placed in a ball mill along with 5kg of 3.2φ bearing balls and ground to obtain a slurry. After grinding was complete, the slurry was sieved through a 37 μm sieve to remove coarse particles, and then excess solvent naphtha was removed by filter pressing to obtain a cake with a heating residue of 90% by mass. The obtained cake was transferred to a vertical mixer, ethyl acetate was added, and after mixing and stirring for 15 minutes, excess solvent naphtha was removed again by filter pressing. Then, in the vertical mixer again, ethyl acetate was added, and after mixing and stirring, the process of removing solvent naphtha by filter pressing was repeated until the heating residue (aluminum solids) was 70% by mass, thereby obtaining aluminum paste A7. At this time, the ethyl acetate was 29.5% by mass, the solvent naphtha was 0.3% by mass, and the oleic acid was 0.2% by mass. The aluminum pigment in aluminum paste A7 was of the non-leafing type, with a D50 average particle size of 20 μm, an average thickness of 0.1 μm, and an aspect ratio of 200.

[0111] (Manufacturing example 8) Using 100g of atomized aluminum powder (atomized powder), 2g of oleic acid, and 500mL of solvent naphtha as raw materials, these were placed in a ball mill along with 5kg of 3.2φ bearing balls and ground to obtain a slurry. After grinding was complete, the slurry was sieved through a 37 μm sieve to remove coarse particles, and then excess solvent naphtha was removed by filter pressing to obtain a cake with a heating residue of 90% by mass. The obtained cake was transferred to a vertical mixer, methyl ethyl ketone was added, and after mixing and stirring for 15 minutes, excess solvent naphtha was removed again by filter pressing. Then, in the vertical mixer again, methyl ethyl ketone was added, and after mixing and stirring, the process of removing solvent naphtha by filter pressing was repeated until the heating residue (aluminum solids) was 70% by mass, thereby obtaining aluminum paste A8. At this time, the methyl ethyl ketone was 29.5% by mass, solvent naphtha was 0.3% by mass, and oleic acid was 0.2% by mass. The aluminum pigment in aluminum paste A8 was of the non-leafing type, with a D50 average particle size of 5 μm, an average thickness of 2 μm, and an aspect ratio of 2.5.

[0112] (Manufacturing example 9) Using 100g of atomized aluminum powder (atomized powder), 2g of oleic acid, and 500mL of solvent naphtha as raw materials, these were placed in a ball mill along with 5kg of 3.2φ bearing balls and ground to obtain a slurry. After grinding was complete, the slurry was sieved through a 37 μm sieve to remove coarse particles, and then excess solvent naphtha was removed by filter pressing to obtain a cake with a heating residue of 90% by mass. The obtained cake was transferred to a vertical mixer, isopropyl alcohol was added, and after mixing and stirring for 15 minutes, excess solvent naphtha was removed again by filter pressing. Then, in the vertical mixer again, isopropyl alcohol was added, and after mixing and stirring, the process of removing solvent naphtha by filter pressing was repeated until the heating residue (aluminum solids) was 70% by mass, thereby obtaining aluminum paste A9. At this time, the isopropyl alcohol content was 29.5% by mass, solvent naphtha was 0.3% by mass, and oleic acid was 0.2% by mass. The aluminum pigment in aluminum paste A9 was of the non-leafing type, with a D50 average particle size of 10 μm, an average thickness of 0.1 μm, and an aspect ratio of 100.

[0113] (Manufacturing example 10) Using 100g of atomized aluminum powder (atomized powder), 2g of oleic acid, and 500mL of solvent naphtha as raw materials, these were placed in a ball mill along with 5kg of 3.2φ bearing balls and ground to obtain a slurry. After grinding was complete, the slurry was sieved through a 37 μm sieve to remove coarse particles, and then excess solvent naphtha was removed by filter pressing to obtain a cake with a heating residue of 90% by mass. The obtained cake was transferred to a vertical mixer, n-propyl alcohol was added, and after mixing and stirring for 15 minutes, excess solvent naphtha was removed again by filter pressing. Then, n-propyl alcohol was added again in the vertical mixer, and after mixing and stirring, the process of removing solvent naphtha by filter pressing was repeated until the heating residue (aluminum solids) was 70% by mass, thereby obtaining aluminum paste A10. At this time, the n-propyl alcohol content was 29.5% by mass, solvent naphtha was 0.3% by mass, and oleic acid was 0.2% by mass. The aluminum pigment in aluminum paste A10 was of the non-leafing type, with a D50 average particle size of 10 μm, an average thickness of 0.1 μm, and an aspect ratio of 100.

[0114] (Manufacturing Example 11) Using 100g of atomized aluminum powder (atomized powder), 2g of oleic acid, and 500mL of solvent naphtha as raw materials, these were placed in a ball mill along with 5kg of 3.2φ bearing balls and ground to obtain a slurry. After grinding was complete, the slurry was sieved through a 37 μm sieve to remove coarse particles, and then excess solvent naphtha was removed by filter pressing to obtain a cake with a heating residue of 90% by mass. The obtained cake was transferred to a vertical mixer, propylene glycol monomethyl ether was added, and after mixing and stirring for 15 minutes, excess solvent naphtha was removed again by filter pressing. Then, in the vertical mixer again, propylene glycol monomethyl ether was added, mixed and stirred, and the process of removing solvent naphtha by filter pressing was repeated until the heating residue (aluminum solids) was 90% by mass, thereby obtaining aluminum paste A11. At this time, the propylene glycol monomethyl ether content was 29.5% by mass, solvent naphtha was 0.3% by mass, and oleic acid was 0.2% by mass. The aluminum pigment in aluminum paste A11 was of the non-leafing type, with a D50 average particle size of 10 μm, an average thickness of 0.1 μm, and an aspect ratio of 100.

[0115] (Manufacturing Example 12) Aluminum paste A12 was obtained in the same manner as aluminum paste A1 of Production Example 1, with a heating residue (aluminum solids) of 70% by mass. At this time, n-propyl acetate was 26.8% by mass, solvent naphtha was 3% by mass, and oleic acid was 0.2% by mass. The aluminum pigment in aluminum paste A12 was of the non-leafing type, with a D50 average particle size of 7 μm, an average thickness of 0.14 μm, and an aspect ratio of 50.

[0116] [Preparation of organic solvent-based ink compositions] Ink G1 (Example 1) 55 parts of LG-FK R medium (urethane resin solution, 20% solids, manufactured by Tokyo Ink Co., Ltd.), 20 parts of aluminum paste A1 (aluminum pigment, 70% solids, D50 average particle size 7 μm, average thickness 0.14 μm, aspect ratio 50), 20 parts of n-propyl acetate, and 5 parts of isopropyl alcohol were stirred in a dissolver for 30 minutes to prepare organic solvent-type ink composition G1 (abbreviated as ink G1). Similarly, organic solvent-type ink compositions for Examples 2 to 22 and Comparative Example 1 were prepared according to the formulations in Tables 1 to 3.

[0117] (Reference example) 55 parts of LG-FK R medium (urethane resin solution, 20% solids, manufactured by Tokyo Ink Co., Ltd.), 20 parts of aluminum paste X1 (BP-280PA, resin-coated aluminum pigment (non-leafing type), 44% solids, D50 average particle size 9 μm, manufactured by Toyo Aluminum Co., Ltd.), 20 parts of n-propyl acetate, and 5 parts of isopropyl alcohol were stirred in a dissolver for 30 minutes to prepare an ink composition X1 (abbreviated as ink X1) using a conventional type of resin-coated aluminum pigment.

[0118] (Reference example) 55 parts of LG-FK R medium (urethane resin solution, 20% solids, manufactured by Tokyo Ink Co., Ltd.), 20 parts of aluminum paste X1 (BP-280PA, resin-coated aluminum pigment (non-leafing type), 44% solids, D50 average particle size 9 μm, manufactured by Toyo Aluminum Co., Ltd.), 5 parts of isopropyl alcohol, 10 parts of n-propyl acetate, and 10 parts of methyl ethyl ketone were stirred in a dissolver for 30 minutes to prepare an ink composition X2 (abbreviated as ink X2) using a conventional type of resin-coated aluminum pigment.

[0119] (Reference example) 55 parts of LG-FK R medium (urethane resin solution, 20% solids, manufactured by Tokyo Ink Co., Ltd.), 20 parts of aluminum paste X2 (TD-690PA, uncoated aluminum pigment (leafing type), 67% solids, D50 average particle size 8 μm, manufactured by Toyo Aluminum Co., Ltd.), 20 parts of n-propyl acetate, and 5 parts of isopropyl alcohol were stirred in a dissolver for 30 minutes to prepare an ink composition X3 (abbreviated as ink X3) using a conventional type of aluminum pigment.

[0120] [Preparation of organic solvent-based ink compositions] Ink H1 (Example 23) 40 parts of LG-FK R medium (urethane resin solution, 20% solids, manufactured by Tokyo Ink Co., Ltd.) and 5 parts of yellow pigment (Pigment Yellow 83) were added and mixed in a paint shaker. Then, 20 parts of aluminum paste A1 (aluminum pigment, 70% solids, D50 average particle size 7 μm, average thickness 0.14 μm, aspect ratio 50), 28 parts of n-propyl acetate, and 7 parts of isopropyl alcohol were stirred in a dissolver for 30 minutes to prepare organic solvent-type ink composition H1 (abbreviated as ink H1). Similarly, organic solvent-type ink composition H2 (abbreviated as ink H2) for Comparative Example 2 was prepared according to the formulation in Table 4.

[0121] (Reference example) In the above-mentioned Example 23, aluminum paste A1 was replaced with aluminum paste X1 (BP-280PA, resin-coated aluminum pigment (non-leafing type), solid content 44%, D50 average particle size 9 μm, manufactured by Toyo Aluminum Co., Ltd.) to prepare an ink composition V1 (abbreviated as ink V1) using a conventional type of resin-coated aluminum pigment.

[0122] 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.

[0123] [Table 1]

[0124] [Table 2]

[0125] [Table 3]

[0126] [Table 4]

[0127] The following were used as gravure inks. 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.)

[0128] [Manufacturing of coated objects] (Example 31) A 150L 40μm laser plate was mounted on a GRAVO-PROOF gravure proofing machine (model number: CM-W, manufactured by Nissho Gravure Co., Ltd.). Ink G1 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 20μm thick stretched polypropylene film, Pyrene P-2161 (abbreviated as OPP, manufactured by Toyobo Co., Ltd.), to a film thickness of 2.0μm, obtaining OPP / ink G1 coated product PR1. Similarly, as shown in Tables 5 to 8, the ink and film thickness were changed to obtain coated materials PR2, PR5 to PR11, PR15 to PR17, PR21 to PR30, and PR101 to PR103, respectively. Furthermore, by changing ink G1 to ink H1 or ink H2, coated products PR18 and PR104 were obtained in the same manner.

[0129] (Reference example) Furthermore, by changing ink G1 to the conventional inks X1 to X3 or ink V1, the conventional reference examples of coated products PRX1 to PRX3 or coated product PRV1 were obtained in the same way.

[0130] (Example 33) Furthermore, the base material is 65g / m 2 Instead of using Ryuo Coat (abbreviated as paper, manufactured by Daio Paper Corporation), which is a coated paper, ink G3 was printed to a film thickness of 2.1 μm in the same manner as in Example 31 to obtain coated product PR3.

[0131] (Reference example) Furthermore, by changing ink G3 to the conventional ink X1, the conventional coated material PRX4 was obtained in the same manner as the reference example.

[0132] (Example 34) Furthermore, the substrate was replaced with GM (abbreviated as OPS, manufactured by Asahi Kasei Corporation), a 20 μm thick styrene (OPS) film, and ink G4 was printed to a film thickness of 1.9 μm in the same manner as in Example 31 to obtain coated product PR4.

[0133] (Reference example) Furthermore, by changing ink G4 to the conventional ink X1, the conventional coated material PRX5 was obtained in the same manner as the reference example.

[0134] (Example 42) Furthermore, the substrate was replaced with E-5102 (abbreviated as PET, manufactured by Toyobo Co., Ltd.), a PET film with a thickness of 12 μm, and ink G1 was printed to a film thickness of 2.0 μm in the same manner as in Example 31 to obtain coated product PR12. Similarly, as shown in Table 8, the ink was changed to obtain coated material PR105.

[0135] (Reference example) Furthermore, by changing ink G1 to the conventional ink X1, the conventional coated material PRX6 was obtained in the same manner.

[0136] (Example 43) Furthermore, the substrate was replaced with Techbarrier LS (abbreviated as VMPET, manufactured by Mitsubishi Chemical Corporation), an aluminum-deposited PET film with a thickness of 12 μm, and ink G1 was printed to a film thickness of 1.9 μm in the same manner as in Example 31 to obtain coated product PR13. Similarly, as shown in Tables 6 and 8, the ink and film thickness were changed to obtain coated materials PR19 to PR20 and coated materials PR106 to PR108, respectively.

[0137] (Reference example) Furthermore, by changing ink G1 to the conventional ink X1, the conventional coated material PRX7 was obtained in the same manner.

[0138] (Example 44) Furthermore, the substrate was replaced with HD200 (abbreviated as BOPE, manufactured by Jindal Films), a biaxially oriented polyethylene film with a thickness of 25 μm, and ink G1 was printed to a film thickness of 2.0 μm in the same manner as in Example 31 to obtain coated product PR14.

[0139] (Reference example) Furthermore, by changing ink G1 to the conventional ink X1, the conventional coated material PRX8 was obtained in the same manner as the reference example.

[0140] (Example 61) 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 engraved 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, and a finisher roll. Black ink K1, cyan ink C1, red ink M1, yellow ink Y1, white ink W1, and ink G1 are each diluted with a solvent (MEK4). After adjusting the viscosity to 15 seconds using a Zahn cup No. 3 with 0 parts of propyl acetate and 20 parts of isopropyl alcohol, 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 ink G1 to the ink pan of unit 6. A doctor blade pressure of 2 kgf / cm was used in all units. 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, blue ink C1 to a thickness of 1.1 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 0.9 μm, and ink G1 to a thickness of 1.9 μm to obtain a coated product PR31 consisting of an OPP / printed layer / ink layer. During printing, the viscosity was kept constant using a viscosity controller (manufactured by Meisei Co., Ltd.). Similarly, as shown in Tables 10 and 11, the ink and film thickness were changed to obtain coated products PR32 to PR33, PR37 to PR45, and PR111 to PR113, respectively.

[0141] (Reference example) Furthermore, by changing ink G1 to the conventional ink X1, the conventional coated material PRX11 was obtained in the same manner.

[0142] (Example 64) Furthermore, the substrate was replaced with E-5102 (abbreviated as PET, manufactured by Toyobo Co., Ltd.), a PET film with a thickness of 12 μm, and ink G1 was printed to a film thickness of 2.0 μm in the same manner as in Example 61 to obtain coated product PR34.

[0143] (Reference example) Furthermore, by changing ink G1 to the conventional ink X1, the conventional coated material PRX12 was obtained in the same manner.

[0144] (Example 65) Furthermore, the substrate was replaced with Techbarrier LS (abbreviated as VMPET, manufactured by Mitsubishi Chemical Corporation), an aluminum-deposited PET film with a thickness of 12 μm, and ink G1 was printed to a film thickness of 1.9 μm in the same manner as in Example 61 to obtain coated product PR35.

[0145] (Reference example) Furthermore, by changing ink G1 to the conventional ink X1, the conventional coated material PRX13 was obtained in the same manner as the reference example.

[0146] (Example 66) Furthermore, the substrate was replaced with HD200 (abbreviated as BOPE, manufactured by Jindal Films), a biaxially oriented polyethylene film with a thickness of 25 μm, and ink G1 was printed to a film thickness of 2.0 μm in the same manner as in Example 61 to obtain coated product PR36.

[0147] (Reference example) Furthermore, by changing ink G1 to the conventional ink X1, the conventional coated material PRX14 was obtained in the same manner as the reference example.

[0148] (Example 81) 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 engraved 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, and a finisher roll. Ink G1, black ink K1, cyan ink C1, red ink M1, yellow ink Y1, and white ink W1 are each diluted with a solvent (MEK4). After adjusting the viscosity to 15 seconds using a Zahn cup No. 3 with 0 parts of propyl acetate and 20 parts of isopropyl alcohol, 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. A doctor blade pressure of 2 kgf / cm was used in all units. 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 ink G1 to a thickness of 2.0 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 a coated product PR51 consisting of an OPP / ink layer / printed layer. During printing, the viscosity was kept constant using a viscosity controller (manufactured by Meisei Co., Ltd.). Similarly, as shown in Tables 13 and 14, the ink and film thickness were changed to obtain coated products PR52 to PR53, PR57 to PR65, and PR114 to PR116, respectively.

[0149] (Reference example) Furthermore, by changing ink G1 to the conventional ink X1, the conventional coated material PRX21 was obtained in the same manner.

[0150] (Example 84) Furthermore, the substrate was replaced with E-5102 (abbreviated as PET, manufactured by Toyobo Co., Ltd.), a PET film with a thickness of 12 μm, and ink G1 was printed to a film thickness of 1.9 μm in the same manner as in Example 81 to obtain coated product PR54.

[0151] (Reference example) Furthermore, by changing ink G1 to the conventional ink X1, the conventional coated material PRX22 was obtained in the same manner as the reference example.

[0152] (Example 85) Furthermore, the substrate was replaced with Techbarrier LS (abbreviated as VMPET, manufactured by Mitsubishi Chemical Corporation), an aluminum-deposited PET film with a thickness of 12 μm, and ink G1 was printed to a film thickness of 2.0 μm in the same manner as in Example 81 to obtain coated product PR55.

[0153] (Reference example) Furthermore, by changing ink G1 to the conventional ink X1, the conventional coated material PRX23 was obtained in the same manner as the reference example.

[0154] (Example 86) Furthermore, the substrate was replaced with HD200 (abbreviated as BOPE, manufactured by Jindal Films), a biaxially oriented polyethylene film with a thickness of 25 μm, and ink G1 was printed to a film thickness of 2.0 μm in the same manner as in Example 81 to obtain coated product PR56.

[0155] (Reference example) Furthermore, by changing ink G1 to the conventional ink X1, the conventional coated material PRX24 was obtained in the same manner.

[0156] [Table 5]

[0157] [Table 6]

[0158] [Table 7]

[0159] [Table 8]

[0160] [Table 9]

[0161] [Table 10]

[0162] [Table 11]

[0163] [Table 12]

[0164] [Table 13]

[0165] [Table 14]

[0166] [Table 15]

[0167] <Adhesion> Adhesive tape (18mm, manufactured by Nichiban Co., Ltd.) was applied to the ink layer surface of the coated materials (the printed layer surface for coated materials PR51 to PR65, and coated materials PR114 to PR116), and then rapidly peeled off at a 90-degree angle. The degree of peeling of the printed surface was visually observed, and the adhesion was evaluated. Materials that did not peel off the printed surface were judged to have good adhesion. Adhesion was evaluated on a three-point scale: ○: no peeling at all, △: slight peeling (no practical problem), ×: clear peeling.

[0168] <Brightness> The surface condition (luminosity) of the coated material was visually observed and evaluated under a standard light source (model: MacbethjudgeII, manufactured by X-Rite). Furthermore, the following comparisons were made between non-leafing aluminum pigments and between leafing aluminum pigments. [Comparison of non-leafing aluminum pigments] Comparison of coated materials PR1-PR16, PR19-PR30, PR101-PR103, PR105-PR108, and coated materials PRX1 or PRX2, and coated materials PRX4-PRX8 prepared using ink composition X1 or ink composition X2, using the same substrate layers. Comparison of coated materials PR18 and PR104 with coated material PRV1 prepared using ink composition V1. Comparison of coated materials PR31-PR45, PR111-PR113, and coated materials PRX11-PRX14 prepared using ink composition X1, using the same substrate layers. Comparison of coated materials PR51-PR65, PR114-PR116, and coated materials PRX21-PRX24 prepared using ink composition X1, using the same substrate layers. [Comparison of leafing-type aluminum pigments] Comparison of coated material PR17 and coated material PRX3 prepared using ink composition X3. A total score was calculated based on the evaluation of coatings, with 10 panelists assigning points to those that showed a brightness level equivalent to conventional reference examples such as coated materials PRX1-PRX8, PRV1, PRX11-PEX14, and PRX21-PRX24, and 0 points to those that showed a brightness level inferior to PRX1-PRX8, PRV1, PRX11-PEX14, and PRX21-PRX24. Brightness was evaluated on a two-point scale: ○: total score of 7 points or higher, ×: less than 7 points.

[0169] In this invention, luminosity is defined as the appearance of gloss when the surface state of the coated material is visually observed. Coated material PR2 (substrate is OPP, corresponding conventional reference example: coated material PRX2), coated material PR3 (substrate is paper, corresponding conventional reference example: coated material PRX4), and coated material PR4 (substrate is OPS, corresponding conventional reference example: coated material PRX5) were configured with front printing and observed from the ink layer side. Coated materials PR41 to PR45 and coated materials PR111 to PR113 (corresponding conventional reference examples: coated materials PRX111 to coated material PRX113), which have a printed layer, were also configured with front printing and observed from the ink layer side. All other coated materials were configured with back printing and observed from the substrate layer side. The coated material of the present invention can achieve a brightness equivalent to that of a coated material made using the conventional reference ink compositions X1 to X3 or ink composition V1.

[0170] [Fabrication of laminates] (Example 101) Takelac A-969V / A-5 (abbreviated as DL, manufactured by Mitsui Chemicals, Inc.) was coated onto the ink layer of coated material PR1 of Example 31 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, a laminate LAM1 of OPP / ink G1 / DL / CPP was obtained. Similarly, by changing the coating material as shown in Tables 16 to 19, laminates LAM2 to LAM8, LAM13 to LAM16, LAM19 to LAM28, and LAM61 to LAM64 were obtained, respectively.

[0171] (Example 109) In Example 42, Takelac A-969V / A-5 (abbreviated as DL, manufactured by Mitsui Chemicals, Inc.) was coated onto the ink layer of coated material PR12 using A-Bar OSP-10 (manufactured by OSG System Products Co., Ltd.), and a 50 μm thick linear low-density polyethylene film, LIX-NP L4102 (abbreviated as PE50, manufactured by Toyobo Co., Ltd.), was laminated to it. After aging at 40°C for 24 hours, a PET / ink G1 / DL / PE50 laminate LAM9 was obtained.

[0172] (Example 110) Takelac A-525 / A-52 (abbreviated as DL, manufactured by Mitsui Chemicals, Inc.) was coated onto the ink layer of coated material PR13 of Example 43 using A-Bar OSP-10 (manufactured by OSG System Products Co., Ltd.), and a 50 μm thick unoriented polypropylene film, Trefan NO ZK207 (abbreviated as RetoCP, manufactured by Toray Film Processing Co., Ltd.), was laminated to it. After aging at 40°C for 48 hours, a laminate LAM10 of VMPET / ink G1 / DL / RetoCP was obtained. Similarly, as shown in Tables 17 and 19, the coating material was changed to obtain laminates LAM17 to LAM18 and LAM66 to LAM68, respectively.

[0173] (Example 111) Takelac A-969V / A-5 (abbreviated as DL, manufactured by Mitsui Chemicals, Inc.) was coated onto the ink layer of coated material PR14 of Example 44 using A-Bar OSP-10 (manufactured by OSG System Products Co., Ltd.), and a 50 μm thick linear low-density polyethylene film, LIX-NP L4102 (abbreviated as PE50, manufactured by Toyobo Co., Ltd.), was laminated to it. After aging at 40°C for 24 hours, a laminate LAM11 of BOPE / ink G1 / DL / PE50 was obtained.

[0174] (Example 112) In Example 42, Takelac A-969V / A-5 (abbreviated as DL, manufactured by Mitsui Chemicals, Inc.) was coated onto the ink layer of coated material PR12 using A-Bar OSP-10 (manufactured by OSG System Products Co., Ltd.), and a 50 μm thick unoriented co-extruded multilayer film, CF film 9501H (Easy Peel Film) (abbreviated as EP, manufactured by Toray Film Processing Co., Ltd.), was laminated to it. After aging at 40°C for 24 hours, a PET / ink G1 / DL / EP laminate LAM12 was obtained. Similarly, as shown in Table 19, the coating material was changed to obtain the laminate LAM65.

[0175] Furthermore, the inks (G2-G4) used for coated materials PR2-PR4 were not laminated because their composition was not suitable for lamination (no laminates were created).

[0176] (Example 131) Takelac A-969V / A-5 (abbreviated as DL, manufactured by Mitsui Chemicals, Inc.) was coated onto the ink layer of coated material PR31 of Example 61 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, a laminate LAM31 consisting of OPP / printing layer / ink G1 / DL / CPP was obtained. Similarly, as shown in Table 20, the coating material was changed to obtain laminates LAM32 to LAM33 and laminates LAM71 to LAM73, respectively.

[0177] (Example 134) In Example 64, Takelac A-969V / A-5 (abbreviated as DL, manufactured by Mitsui Chemicals, Inc.) was coated onto the ink layer of coated material PR34 using A-Bar OSP-10 (manufactured by OSG System Products Co., Ltd.), and a 50 μm thick linear low-density polyethylene film, LIX-NP L4102 (abbreviated as PE50, manufactured by Toyobo Co., Ltd.), was laminated to it. After aging at 40°C for 24 hours, a laminate LAM34 consisting of PET / printing layer / ink G1 / DL / PE50 was obtained.

[0178] (Example 135) In Example 65, Takelac A-525 / A-52 (abbreviated as DL, manufactured by Mitsui Chemicals, Inc.) was applied to the ink layer of coated material PR35 using A-Bar OSP-10 (manufactured by OSG System Products Co., Ltd.), and a 50 μm thick unoriented polypropylene film, Trefan NO ZK207 (abbreviated as RetoCP, manufactured by Toray Film Processing Co., Ltd.), was laminated to it. After aging at 40°C for 48 hours, a laminate LAM35 consisting of VMPET / printing layer / ink G1 / DL / RetoCP was obtained.

[0179] (Example 136) In Example 66, Takelac A-969V / A-5 (abbreviated as DL, manufactured by Mitsui Chemicals, Inc.) was coated onto the ink layer of coated material PR36 using A-Bar OSP-10 (manufactured by OSG System Products Co., Ltd.), and a 50 μm thick linear low-density polyethylene film, LIX-NP L4102 (abbreviated as PE50, manufactured by Toyobo Co., Ltd.), was laminated to it. After aging at 40°C for 24 hours, a laminate LAM36 consisting of BOPE / printing layer / ink G1 / DL / PE50 was obtained.

[0180] (Example 141) In Example 81, Takelac A-969V / A-5 (abbreviated as DL, manufactured by Mitsui Chemicals, Inc.) was coated onto the white ink layer of coated material PR51 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, a laminate LAM41 consisting of OPP / ink G1 / printing layer / DL / CPP was obtained. Similarly, as shown in Table 21, the coating material was changed to obtain laminates LAM42 to LAM43 and laminates LAM74 to LAM76, respectively.

[0181] (Example 144) On the white ink layer of the coated product PR54 of Example 84, Tacklac A-969V / A-5 (abbreviation: DL, manufactured by Mitsui Chemicals, Inc.) was coated with an A-Bar OSP-10 (manufactured by OSG Systems Products Co., Ltd.), and then laminated with LIX-NP L4102 (abbreviation: PE50, manufactured by Toyobo Co., Ltd.), a linear low-density polyethylene film with a thickness of 50 μm. After that, aging was carried out at 40°C for 24 hours to obtain a laminate LAM44 of PET / Ink G1 / Printing layer / DL / PE50.

[0182] (Example 145) On the white ink layer of the coated product PR55 of Example 85, Tacklac A-525 / A-52 (abbreviation: DL, manufactured by Mitsui Chemicals, Inc.) was coated with an A-Bar OSP-10 (manufactured by OSG Systems Products Co., Ltd.), and then laminated with Trephan NO ZK207 (abbreviation: Ret CP, manufactured by Toray Film Processing Co., Ltd.), an unstretched polypropylene film with a thickness of 50 μm. After that, aging was carried out at 40°C for 48 hours to obtain a laminate LAM45 of VMPET / Ink G1 / Printing layer / DL / Ret CP.

[0183] (Example 146) On the white ink layer of the coated product PR56 of Example 86, Tacklac A-969V / A-5 (abbreviation: DL, manufactured by Mitsui Chemicals, Inc.) was coated with an A-Bar OSP-10 (manufactured by OSG Systems Products Co., Ltd.), and then laminated with LIX-NP L4102 (abbreviation: PE50, manufactured by Toyobo Co., Ltd.), a linear low-density polyethylene film with a thickness of 50 μm. After that, aging was carried out at 40°C for 24 hours to obtain a laminate LAM46 of BOPE / Ink G1 / Printing layer / DL / PE50.

[0184]

Table 16

[0185]

Table 17

[0186] [Table 18]

[0187] [Table 19]

[0188] [Table 20]

[0189] [Table 21]

[0190] <Lamination Strength> 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 layer / organic solvent-type gravure ink layer interface, at a tensile speed of 300mm / min. The maximum load at the time of peeling was measured as the laminate strength. A higher laminate strength indicated better lamination properties. The laminate strength was evaluated in three stages: ○: 80g or more, △: 50g or more, less than 80g, and ×: less than 50g.

[0191] <Suitable for retort packaging> Two retort-type laminates (excluding laminates LAM12 and LAM65) are subjected to a load of 3 kgf / cm². 2The layers were heat-sealed at 180°C for 1 second to obtain a 15cm x 10cm packaging bag with an opening. A mixture of salad oil / ketchup / vinegar (1 / 1 / 1) was filled into this packaging bag, and the opening was heat-sealed under the same conditions as above to create a new packaging bag. This packaging bag was retorted at 120°C for 30 minutes using a hot water shower method, and the appearance of the packaging bag was visually inspected to check for any areas where the printed layer had peeled off and lifted. The evaluation was done in two stages: ○: no change at all, ×: lifting observed. Laminates that were not retortable were not evaluated for retort suitability and are indicated as "-" in the table.

[0192] <Suitable for retort packaging> For laminates LAM12 and LAM65, water is placed in a polypropylene container, and the heat-sealed layer surface (inner side) of each laminate is placed on the top of the opening of the polypropylene container at a rate of 3 kgf / cm². 2 A packaging body was created using a laminate as a lid material by bonding the laminate in a ring shape using a hot-press seal (ring seal) at 220°C for 1 second. This packaging body was retorted at 120°C for 30 minutes using a hot water shower method, and the appearance of the laminate used as the lid material was visually observed and evaluated for any areas of lifting due to delamination of the printed layer. The evaluation was on a two-point scale: ○: no change at all, ×: lifting observed.

[0193] According to Tables 1 to 21, the coated materials using inks G1 to G22 from Examples 1 to 22 and ink H1 from Example 23 showed good adhesion and brightness, as evidenced by the results from Examples 31 to 60, 61 to 75, and 81 to 95. Furthermore, the laminates using inks G1 to G22 from Examples 1 to 22 and ink H1 from Example 23 showed good laminate strength, as evidenced by the results from Examples 101 to 128. In addition, the laminates with a retort structure showed good retort suitability, as evidenced by the results from Examples 110, 112, 117 to 118, 135, and 145. Coated materials using Ink G23 of Comparative Example 1 and Ink H2 of Comparative Example 2, which contain a high amount of Solvent A (high-boiling point solvent component), showed slightly inferior adhesion and inferior brightness, as seen in the results for Comparative Examples 10, 13, 14-15, 18, and 21. Furthermore, coated materials with film thicknesses outside the specified range showed inferior adhesion or brightness, as seen in the results for Comparative Examples 11-12, 16-17, 19-20, and 22-23. In addition, laminates using Ink G23 of Comparative Example 1 and Ink H2 of Comparative Example 2, which contain a high amount of Solvent A (high-boiling point solvent component), showed inferior laminate strength, as seen in the results for Comparative Examples 31, 34, 35-36, 41, and 44. Moreover, laminates with a retort structure showed poor retort suitability, as seen in the results for Comparative Examples 35-38. Furthermore, it was clear from the results of Comparative Examples 32-33, 37-38, 42-43, and 45-46 that laminates with film thicknesses outside the specified range exhibited inferior laminate strength. Therefore, by replacing the high-boiling-point solvent component (solvent with a boiling point of 130-510°C) in the aluminum paste of conventional gravure printing inks with a solvent that has a relatively lower boiling point, the amount of high-boiling-point solvent component is reduced, which reduces the environmental burden. In addition, it is possible to achieve coated products with good adhesion and brightness to the substrate layer of the organic solvent-type gravure ink composition, as well as laminates with excellent laminate strength and retort resistance.

Claims

1. In a coated product having an ink layer with a thickness of 0.3 to 5 μm made of an organic solvent-type gravure ink composition on at least one surface of a substrate layer, The aforementioned organic solvent-type gravure ink composition comprises an aluminum pigment satisfying all of the following (a) to (d), solvent A, solvent B, solvent C, and a grinding aid. The solvent A is a solvent with a boiling point of 130 to 510°C. The solvent B is a solvent with a relatively lower boiling point than the solvent A, and is at least one selected from n-propyl acetate, ethyl acetate, methyl ethyl ketone, isopropyl alcohol, n-propyl alcohol, and propylene glycol monomethyl ether. The solvent C is an organic solvent for gravure inks, The aforementioned grinding aid is at least one selected from oleic acid and stearic acid. Furthermore, when the total amount of the organic solvent-type gravure ink composition is 100% by mass, The aluminum pigment is present in an amount of 3 to 50% by mass. The solvent A is 0.01 to 0.5% by mass, The aforementioned grinding aid is 0.01 to 0.3% by mass, A coated article characterized in that the total amount of solvent B and solvent C is 45 to 90% by mass. (a) The raw material aluminum powder is atomized powder. (b) Not coated with resin. (c) The average thickness is 0.1 to 2 μm. (d) The aspect ratio is between 2.5 and 200.

2. In a laminate having an ink layer with a thickness of 0.3 to 5 μm made of an organic solvent-type gravure ink composition on at least one surface of a substrate layer, and a sealant layer or sealing layer on the ink layer, The aforementioned organic solvent-type gravure ink composition comprises an aluminum pigment satisfying all of the following (a) to (d), solvent A, solvent B, solvent C, and a grinding aid. The solvent A is a solvent with a boiling point of 130 to 510°C. The solvent B is a solvent with a relatively lower boiling point than the solvent A, and is at least one selected from n-propyl acetate, ethyl acetate, methyl ethyl ketone, isopropyl alcohol, n-propyl alcohol, and propylene glycol monomethyl ether. The solvent C is an organic solvent for gravure inks, The aforementioned grinding aid is at least one selected from oleic acid and stearic acid. Furthermore, when the total amount of the organic solvent-type gravure ink composition is 100% by mass, The aluminum pigment is present in an amount of 3 to 50% by mass. The solvent A is 0.01 to 0.5% by mass, The aforementioned grinding aid is 0.01 to 0.3% by mass, A laminate characterized in that the total amount of solvent B and solvent C is 45 to 90% by mass. (a) The raw material aluminum powder is atomized powder. (b) Not coated with resin. (c) The average thickness is 0.1 to 2 μm. (d) The aspect ratio is between 2.5 and 200.

3. The process of preparing the substrate layer, A method for manufacturing a coated product, comprising a gravure printing step of printing an ink layer made of an organic solvent-type gravure ink composition onto at least one of the substrate layers to a thickness of 0.3 to 5 μm, The aforementioned organic solvent-type gravure ink composition comprises an aluminum pigment satisfying all of the following (a) to (d), solvent A, solvent B, solvent C, and a grinding aid. The solvent A is a solvent with a boiling point of 130 to 510°C. The solvent B is a solvent with a relatively lower boiling point than the solvent A, and is at least one selected from n-propyl acetate, ethyl acetate, methyl ethyl ketone, isopropyl alcohol, n-propyl alcohol, and propylene glycol monomethyl ether. The solvent C is an organic solvent for gravure inks, The aforementioned grinding aid is at least one selected from oleic acid and stearic acid. Furthermore, when the total amount of the organic solvent-type gravure ink composition is 100% by mass, The aluminum pigment is present in an amount of 3 to 50% by mass. The solvent A is 0.01 to 0.5% by mass, The aforementioned grinding aid is 0.01 to 0.3% by mass, A method for manufacturing a coated product, characterized in that the total amount of solvent B and solvent C is 45 to 90% by mass. (a) The raw material aluminum powder is atomized powder. (b) Not coated with resin. (c) The average thickness is 0.1 to 2 μm. (d) The aspect ratio is between 2.5 and 200.

4. The process of preparing the substrate layer, A gravure printing process in which an ink layer made of an organic solvent-type gravure ink composition is printed on at least one of the substrate layers to a thickness of 0.3 to 5 μm, A method for manufacturing a laminate, comprising a lamination step to create a sealant layer on the ink layer or a coating step to create a seal layer, The aforementioned organic solvent-type gravure ink composition comprises an aluminum pigment satisfying all of the following (a) to (d), solvent A, solvent B, solvent C, and a grinding aid. The solvent A is a solvent with a boiling point of 130 to 510°C. The solvent B is a solvent with a relatively lower boiling point than the solvent A, and is at least one selected from n-propyl acetate, ethyl acetate, methyl ethyl ketone, isopropyl alcohol, n-propyl alcohol, and propylene glycol monomethyl ether. The solvent C is an organic solvent for gravure inks, The aforementioned grinding aid is at least one selected from oleic acid and stearic acid. Furthermore, when the total amount of the organic solvent-type gravure ink composition is 100% by mass, The aluminum pigment is present in an amount of 3 to 50% by mass. The solvent A is 0.01 to 0.5% by mass, The aforementioned grinding aid is 0.01 to 0.3% by mass, A method for producing a laminate, characterized in that the total amount of solvent B and solvent C is 45 to 90% by mass. (a) The raw material aluminum powder is atomized powder. (b) Not coated with resin. (c) The average thickness is 0.1 to 2 μm. (d) The aspect ratio is between 2.5 and 200.

5. A label characterized by being made using the coated material described in claim 1.

6. A packaging body characterized by being made using the laminate described in claim 2.

7. In an organic solvent-type gravure ink composition for use in a coated product having an ink layer with a thickness of 0.3 to 5 μm on at least one surface of a substrate layer, The aforementioned organic solvent-type gravure ink composition comprises an aluminum pigment satisfying all of the following (a) to (d), solvent A, solvent B, solvent C, and a grinding aid. The solvent A is a solvent with a boiling point of 130 to 510°C. The solvent B is a solvent with a relatively lower boiling point than the solvent A, and is at least one selected from n-propyl acetate, ethyl acetate, methyl ethyl ketone, isopropyl alcohol, n-propyl alcohol, and propylene glycol monomethyl ether. The solvent C is an organic solvent for gravure inks, The aforementioned grinding aid is at least one selected from oleic acid and stearic acid. Furthermore, when the total amount of the organic solvent-type gravure ink composition is 100% by mass, The aluminum pigment is present in an amount of 3 to 50% by mass. The solvent A is 0.01 to 0.5% by mass, The aforementioned grinding aid is 0.01 to 0.3% by mass, An organic solvent-type gravure ink composition characterized in that the total amount of solvent B and solvent C is 45 to 90% by mass. (a) The raw material aluminum powder is atomized powder. (b) Not coated with resin. (c) The average thickness is 0.1 to 2 μm. (d) The aspect ratio is between 2.5 and 200.

8. In an organic solvent-type gravure ink composition for use in a laminate having an ink layer with a thickness of 0.3 to 5 μm on at least one surface of a substrate layer, and a sealant layer on the ink layer, The aforementioned organic solvent-type gravure ink composition comprises an aluminum pigment satisfying all of the following (a) to (d), solvent A, solvent B, solvent C, and a grinding aid. The solvent A is a solvent with a boiling point of 130 to 510°C. The solvent B is a solvent with a relatively lower boiling point than the solvent A, and is at least one selected from n-propyl acetate, ethyl acetate, methyl ethyl ketone, isopropyl alcohol, n-propyl alcohol, and propylene glycol monomethyl ether. The solvent C is an organic solvent for gravure inks, The aforementioned grinding aid is at least one selected from oleic acid and stearic acid. Furthermore, when the total amount of the organic solvent-type gravure ink composition is 100% by mass, The aluminum pigment is present in an amount of 3 to 50% by mass. The solvent A is 0.01 to 0.5% by mass, The aforementioned grinding aid is 0.01 to 0.3% by mass, An organic solvent-type gravure ink composition characterized in that the total amount of solvent B and solvent C is 45 to 90% by mass. (a) The raw material aluminum powder is atomized powder. (b) Not coated with resin. (c) The average thickness is 0.1 to 2 μm. (d) The aspect ratio is between 2.5 and 200.

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