JP2021066031A - Laminate film, packaging bag, method for producing laminate film, and method for producing packaging bag - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated film, a packaging bag, a method for producing a laminated film, and a method for producing a packaging bag, which can suppress deterioration of appearance quality. SOLUTION: A gas barrier film layer 11, a first solvent-free adhesive layer 13, an intermediate base material layer 14, a second solvent-free adhesive layer 15, and a thermoplastic resin layer 16 are provided and adhered to each other. The adhesive forming the layer is a two-component curable urethane-based solventless adhesive containing a partially end-acid-modified polyol component and a polyisocyanate component, and the polyisocyanate component is an aliphatic poly. It is a mixture of isocyanate and aromatic polyisocyanate. [Selection diagram] Fig. 1

Description

The present invention relates to a laminated film, a packaging bag, a method for producing a laminated film, and a packaging bag having an adhesive layer formed from a two-component curable urethane-based adhesive between a gas barrier film layer and a thermoplastic resin layer. Regarding the manufacturing method.

The laminated film in which the thermoplastic resin layer and the gas barrier film layer are bonded by an adhesive layer is made into a packaging bag for accommodating foods, cosmetics, pharmaceuticals, etc. through heat welding between the thermoplastic layers (Patent Document 1). .. Even in a resistant packaging bag such as a packaging material for retort heat sterilization, a two-component curable urethane-based adhesive is usually used as the adhesive for forming the adhesive layer. The organic solvent contained in the two-component curable urethane-based adhesive lowers the environmental compatibility of the laminated film and the packaging bag from the viewpoint of VOC (Volatile Organic Compounds) emissions.

Japanese Unexamined Patent Publication No. 2011-46006

On the other hand, in the two-component curing type urethane solvent-free adhesive that does not contain an organic solvent, the viscosity is reduced by reducing the molecular weight of the main agent or the like to the extent that the adhesive can be applied without using an organic solvent. There is. The decrease in the initial cohesive force of the main agent, etc. due to the reduction in molecular weight enables coating without using an organic solvent, but also leads to a longer curing period for obtaining adhesive strength, which is generated during the curing period. The laminated film is given a speckled appearance such as a pear-skin-like or yuzu-skin-like appearance due to the fine air bubbles. In particular, in a laminated film provided with a gas barrier film layer in which fine bubbles are difficult to escape, deterioration in appearance quality is remarkable.

An object of the present invention is to provide a laminated film, a packaging bag, a method for producing a laminated film, and a method for producing a packaging bag, which can suppress deterioration of appearance quality.

The laminated film for solving the above problems includes a gas barrier film layer, a thermoplastic resin layer, an intermediate base material layer located between the gas barrier film layer and the thermoplastic resin layer, the gas barrier film layer and the above. The first solvent-free adhesive layer located between the intermediate base material layer, the second solvent-free adhesive layer located between the intermediate base material layer and the thermoplastic resin layer, and the gas barrier film layer. A water-based ink layer located between the first solvent-free adhesive layer is provided. The water-based ink layer contains a polyurethane resin and an water-based cross-linking agent, and the adhesive forming each adhesive layer is a two-component curing containing a partially end-acid-modified polyol component and a polyisocyanate component. It is a type urethane-based solvent-free adhesive, and the polyisocyanate component is a mixture of an aliphatic polyisocyanate and an aromatic polyisocyanate.

A method for producing a laminated film for solving the above problems is to use a gas barrier film layer, a water-based ink layer, a first solvent-free adhesive layer, an intermediate base material layer, a second solvent-free adhesive layer, and a thermoplastic resin layer. A method for producing a laminated film in which the laminated films are arranged in this order, wherein a water-based ink layer is formed on the gas barrier film layer by printing with ink, and the gas barrier film layer provided with the water-based ink layer and the intermediate base material layer are used. Is bonded by coating with a two-component curable urethane-based solvent-free adhesive, and the intermediate base material layer and the thermoplastic resin layer are bonded to each other with a two-component curable urethane-based solvent-free adhesive. Includes sticking by coating. The ink is a water-based ink containing a polyurethane-based resin and an aqueous cross-linking agent, and the two-component curable urethane-based solvent-free adhesive contains a partially end-acid-modified polyol component and a polyisocyanate. The polyisocyanate component is a mixture of an aliphatic polyisocyanate and an aromatic polyisocyanate.

According to each of the above configurations, since the adhesive layer is formed by using a two-component curable urethane-based solvent-free adhesive, it is possible to improve the environmental compatibility of the laminated film. Further, in the configuration in which the water-based ink layer exists between the gas barrier film layer and the first solvent-free adhesive layer, the water or water-based solvent remaining in the water-based ink layer and the adhesive of the first solvent-free adhesive layer are subordinate to each other. The reaction may generate bubbles between the gas barrier film layer and the adhesive layer. In this respect, since the water-based ink layer contains the polyurethane resin and the water-based cross-linking agent, a side reaction between the water and solvent components remaining in the water-based ink layer and the adhesive of the first solvent-free adhesive layer, and eventually the gas barrier film layer. It is possible to suppress the generation of air bubbles between the and the adhesive layer. In addition, since the polyisocyanate component constituting the adhesive is a mixture of the aliphatic polyisocyanate and the aromatic polyisocyanate, it is possible to prevent the laminated film from exhibiting a speckled appearance.

In the laminated film, the aqueous cross-linking agent is a carbodiimide compound, the polyol component is a polyester polyol, the aliphatic polyisocyanate is hexamethylene diisocyanate, and the aromatic polyisocyanate is xylylene diisocyanate. It may be isocyanate.

In the method for producing a laminated film, the aqueous cross-linking agent is a carbodiimide compound, the polyol component is a polyester polyol, the aliphatic polyisocyanate is hexamethylene diisocyanate, and the aromatic polyisocyanate is. , Xylylene diisocyanate may be used.

In the laminated film, the amount of the alcohol solvent remaining in the water-based ink layer ^{may be 20 mg / m 2} or less. Further, in the laminated film, the amount of water remaining in the water-based ink layer ^{may be 100 mg / m 2} or less. According to each of these configurations, the effectiveness of suppressing the formation of air bubbles between the gas barrier film layer and the first solvent-free adhesive layer can be enhanced.

In the laminated film, the gas barrier film layer includes a base film layer, a barrier layer located between the base film layer and the first solvent-free adhesive layer, and the base film layer and the barrier layer. A primer layer located between the primer layer and a metal oxide layer located between the primer layer and the barrier layer may be provided. The material constituting the barrier layer is a condensate of a metal alkoxide, a condensate of a hydrolysis product of a metal alkoxide, a condensate of alkoxysilylalkyl isocyanurate, and a coating of a water-soluble polymer having a hydroxyl group. It may contain any one selected from the group consisting of dried membranes.

In the laminated film, the gas barrier film layer includes a base film layer, a barrier layer located between the base film layer and the first solvent-free adhesive layer, and the base film layer and the barrier layer. A primer layer located between the primer layer and a metal oxide layer located between the primer layer and the barrier layer may be provided. Then, the primer layer may contain a reaction product of either one of the trialkoxysilane and the hydrolysis product of the trialkoxysilane, the acrylic polyol, and the isocyanate compound.

In the laminated film, the gas barrier film layer is a barrier layer located between the base film layer, the base film layer, and the first solvent-free adhesive layer, and is a polycarboxylic acid-based polymer. The barrier layer including the barrier layer may be provided.

In the laminated film, the gas barrier film layer is a barrier layer located between the base film layer, the base film layer, and the first solvent-free adhesive layer, and is composed of a metal oxide and a phosphorus compound. The barrier layer containing the hydrolysis product of the above may be provided.

In the method for producing a laminated film, the coating temperature of the two-component curable urethane-based solvent-free adhesive is such that the cone-plate viscosity after 45 minutes from mixing is 3500 mPa · s or more and 6000 mPa · s or less. It may be the temperature.

According to the above-mentioned method for producing a laminated film, the adhesive can be smoothed to the extent that deterioration of the appearance quality of the laminated film can be suppressed, and in addition, the pot life, which is the pot life, is excessively shortened. It is also possible to suppress.

The packaging bag for solving the above problems is a packaging bag in which the thermoplastic resin layers of the laminated film are laminated so as to face each other and sealed by heat welding of the thermoplastic resin layers, and the laminated film is sealed. However, it is the above-mentioned laminated film.

A method for manufacturing a packaging bag for solving the above problems is to manufacture a laminated film, and the thermoplastic resin layers included in the laminated film are laminated so as to face each other, and the thermoplastic resin layers are heat-welded to each other. It is a method of manufacturing a packaging bag including sealing a packaging bag by means of, and manufacturing the laminated film is the above-mentioned method of manufacturing a laminated film.

According to the method for producing a laminated film, a packaging bag, and a laminated film, and the method for producing a packaging bag in the present invention, deterioration of appearance quality can be suppressed.

The cross-sectional view which shows the layer structure in one Embodiment of a laminated film. The plan view which shows the planar structure in one Embodiment of a packaging bag. The process diagram in one Embodiment of the manufacturing method of a laminated film. A graph showing the relationship between cone plate viscosity and elapsed time. The image figure which shows the binarized image of the microscope image which imaged the laminated film. The image figure which shows the binarized image of the microscope image which imaged the laminated film.

An embodiment of a laminated film, a packaging bag, a method for manufacturing a laminated film, and a method for manufacturing a packaging bag will be described with reference to FIGS. 1 to 6.
[First layer configuration]
As shown in FIG. 1, the laminated film includes (A) gas barrier film layer 11 / (B) water-based ink layer 12 / (C) first solvent-free adhesive layer 13 / (D) intermediate base material layer 14 / (E). ) The second solvent-free adhesive layer 15 / (F) has a layer structure described as a thermoplastic resin layer 16. That is, the laminated film includes a gas barrier film layer 11, a water-based ink layer 12, a first solvent-free adhesive layer 13, an intermediate base material layer 14, a second solvent-free adhesive layer 15, and a thermoplastic resin layer 16.

The water-based ink layer 12 is located between the gas barrier film layer 11 and the first solvent-free adhesive layer 13. The intermediate base material layer 14 is located between the first solvent-free adhesive layer 13 and the second solvent-free adhesive layer 15. The water-based ink layer 12, the first solvent-free adhesive layer 13, the intermediate base material layer 14, and the second solvent-free adhesive layer 15 are located between the gas barrier film layer 11 and the thermoplastic resin layer 16. The water-based ink layer 12 and the intermediate base material layer 14 are joined by a first solvent-free adhesive layer 13. The intermediate base material layer 14 and the thermoplastic resin layer 16 are joined by a second solvent-free adhesive layer 15.

(A) Gas barrier film layer 11
The gas barrier film layer 11 has a layer structure described as (A1) base film layer / (A2) primer layer / (A3) metal oxide layer / (A4) barrier layer. That is, the gas barrier film layer 11 includes a base film layer, a primer layer, a metal oxide layer, and a barrier layer. The primer layer is located between the base film layer and the barrier layer. The metal oxide layer is located between the primer layer and the barrier layer. The barrier layer is located between the base film layer and the first solvent-free adhesive layer 13. The base film layer and the metal oxide layer are joined by a primer layer.

(A1) Base film layer The base film layer has a single-layer structure made of one resin film or a laminated structure made of two or more resin films. The thickness of the base film layer can be appropriately changed according to various resistances and processability required for the laminated film, and is, for example, 3 μm or more and 200 μm or less. From the viewpoint of increasing the flexibility of the packaging bag, the thickness of the base film layer is preferably 6 μm or more and 30 μm or less.

The material of the resin film constituting the base film layer is, for example, a polyolefin resin, a polyamide resin, a polyester resin, a cyclic olefin resin, and a hydroxyl group-containing polymer. The polyolefin-based resin is, for example, polyethylene terephthalate, polyethylene naphthalate, polyethylene-2,6-naphthalate, polybutylene terephthalate, and copolymers thereof, polyethylene, and polypropylene. The hydroxyl group-containing polymer is, for example, polyvinyl alcohol and an ethylene-vinyl alcohol copolymer. The material constituting the resin film is, for example, one kind selected from the group consisting of a polyolefin-based resin, a polyamide-based resin, and a hydroxyl group-containing polymer, or a combination of two or more kinds.

The resin film constituting the base film layer may be a stretched film or a non-stretched film. From the viewpoint of excellent mechanical strength and dimensional stability, the resin film is preferably a stretched film. The stretched film is a uniaxially stretched film or a biaxially stretched film.

(A2) Primer layer The primer layer has various adhesion functions such as a chemical adsorption function and an anchor function, and enhances the adhesion between the base film layer and the metal oxide layer. The material constituting the primer layer includes, for example, one of a trialkoxysilane and a hydrolysis product of the trialkoxysilane, and a reaction product of an acrylic polyol and an isocyanate compound.

Trialkoxysilanes represented by the general formula _{^{R 1 Si (OR 2) 3}} . R ¹ is an alkyl group having an alkyl group, a vinyl group, an alkyl group containing an isocyanate group, an alkyl group containing a glycidoxy group, and an epoxy group. The ^{alkyl group contained in R 1} may be a linear alkyl group, a branched chain alkyl group, or a cyclic alkyl group. R ¹ can be appropriately changed according to the material constituting the base film layer and the metal oxide layer. OR ² is a hydrolyzable alkoxy group such as a methoxy group, an ethoxy group, and an ethoxymethoxy group. The hydrolysis product of trialkoxysilane is obtained, for example, by adding an acid or an alkali to the trialkoxysilane to hydrolyze the trialkoxysilane. The trialkoxysilane is, for example, one kind selected from the above-mentioned compounds, or a combination of two or more kinds.

The trialkoxysilanes are, for example, ethyltrimethoxysilane, vinyltrimethoxysilane, isocyanatepropyltriethoxysilane, γ-isocyanoxidetrimethoxysilane, glycidoxypropyltrimethoxysilane, and epoxycyclohexylethyltrimethoxysilane. Among these, the trialkoxysilane is preferably isocyanatepropyltriethoxysilane containing an isocyanate group or γ-isocyanatepropyltrimethoxysilane. Further, the trialkoxysilane is preferably a glycidoxytrimethoxysilane having a glycidoxy group or an epoxycyclohexylethyltrimethoxysilane containing an epoxy group.

The acrylic polyol is a homopolymer of an acrylic acid derivative monomer or a copolymer of an acrylic acid derivative monomer and styrene. The copolymer of the acrylic acid derivative monomer has a hydroxyl group at the terminal and contains a compound that has reacted with the isocyanate group of the isocyanate compound. Acrylic acid derivative monomers are, for example, ethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxybutyl methacrylate.

The hydroxyl value of the acrylic polyol is preferably 5 KOH mg / g or more and 200 KOH mg / g or less from the viewpoint of enhancing the reactivity between the acrylic polyol and the isocyanate compound. The ratio (MA / MO) of the mass (MA) of the acrylic polyol to the mass (MO) of the trialkoxysilane is preferably 1/1 or more and 100/1 or less, preferably 2/15 or more and 50/1 or less. More preferably.

The isocyanate compound has two or more isocyanate groups and reacts with an acrylic polyol to form a urethane bond. The isocyanate compound functions as a cross-linking agent for enhancing the adhesion between the base film layer and the metal oxide layer.

The isocyanate compound is, for example, an aromatic isocyanate compound or an aliphatic isocyanate compound. The isocyanate compound is, for example, an aromatic isocyanate compound or a polymer of an aliphatic isocyanate compound and a polyol. The isocyanate compound is a derivative produced from a polymer of an aromatic isocyanate compound, an aliphatic isocyanate compound, and a polyol. The isocyanate compound is, for example, one kind selected from the above-mentioned ones, or a combination of two or more kinds.

Aromatic isocyanate compounds include, for example, tolylene diisocyanate and diphenylmethane diisocyanate. The aliphatic isocyanate compound is, for example, xylylene diisocyanate or hexalylene diisocyanate.

The primer layer is formed by reacting either trialkoxysilane or a hydrolysis product of trialkoxysilane with an acrylic polyol and an isocyanate compound in a solvent.

The solvent may be any solution as long as each component can be dissolved and diluted. The solvent is, for example, an ester solvent, an alcohol solvent, a ketone solvent, and an aromatic hydrocarbon solvent. The ester solvent is, for example, ethyl acetate or butyl acetate. Alcohol-based solvents are, for example, metanol, ethanol, and isopropyl alcohol. The ketone solvent is, for example, methyl ethyl ketone. The aromatic hydrocarbon solvent is, for example, toluene or xylene. The solvent is one selected from the above, or a combination of two or more.

A catalyst for promoting the reaction between the trialkoxysilane and the acrylic polyol may be used. From the viewpoint of increasing reactivity and obtaining polymerization stability, the catalyst is preferably a tin compound such as tin chloride, tin oxychloride, and tin alkoxide. The catalyst may be added directly to the reaction solution at the time of blending each component, or may be added to the reaction solution as a solution such as methanol.

Further, a metal alkoxide for stabilizing the reaction in the primer layer or a hydrolysis product of the metal alkoxide may be used. The metal atom constituting the metal alkoxide is Si, Al, Ti, or Zr. From the viewpoint of stable presence in an aqueous solvent, the metal alkoxide is preferably tetraethoxysilane, tripropoxyaluminum, or a mixture thereof. The hydrolysis product of the metal alkoxide is similar to the method for obtaining the hydrolysis product of trialkoxysilane. The production of the hydrolysis product of the metal alkoxide may be simultaneous with the production of the hydrolysis product of the trialkoxysilane, or may be separate from the production of the hydrolysis product of the trialkoxysilane.

Further, the primer layer may contain various additives. Additives are, for example, curing accelerators, antioxidants, leveling agents, flow modifiers, catalysts, cross-linking reaction accelerators, and fillers. Curing accelerators are, for example, tertiary amines, imidazole derivatives, metal salt compounds of carboxylic acids, quaternary ammonium salts, and quaternary phosphonium salts. Antioxidants are, for example, phenol-based, sulfur-based, and phosphite-based.

One example of a method for forming a primer layer is to mix an acrylic polyol and an isocyanate compound in a solution obtained by hydrolyzing trialkoxysilane or a solution obtained by hydrolyzing trialkoxysilane with a metal alkoxide in the presence of a catalyst. Then, a coating liquid is generated. Next, the coating liquid is applied to the base film layer, and the coating film is dried to form a primer layer.

Another example of a method for forming a primer layer is to add an isocyanate compound to a mixture of a trialkoxysilane and an acrylic polyol in a solvent in which a catalyst and a metal alkoxide are present, and mix the mixture. Alternatively, in a solvent in which a catalyst and a metal alkoxide are present, a trialkoxysilane and an acrylic polyol are mixed, and then a hydrolysis reaction is further carried out, and an isocyanate compound is added to the solution after the hydrolysis reaction to prepare a coating solution. Generate. Next, the coating liquid is applied to the base film layer, and the coating film is dried to form a primer layer.

The method of applying the coating liquid is, for example, a dipping method, a roll coating, a gravure coating, a reverse coating, an air knife coating, a comma coating, a die coating, a screen printing method, a spray coating, and a gravure offset method.

The method of drying the coating film may be any method of evaporating the solvent from the coating liquid. The method for drying the coating film is, for example, hot air drying, hot roll drying, high frequency irradiation, infrared irradiation, and ultraviolet irradiation. Two or more of the above-mentioned methods may be used for drying the coating liquid.

(A3) Metal Oxide Layer The metal oxide layer is composed of a metal oxide. The metal oxides are, for example, silicon oxide and aluminum oxide. The metal oxide is preferably aluminum oxide. The method for forming the metal oxide layer is, for example, a vacuum vapor deposition method or a sputtering method.

The thickness of the metal oxide layer is preferably 10 nm or more and 50 nm or less, and more preferably 15 nm or more and 30 nm or less. When the thickness of the metal oxide layer is 10 nm or more, the barrier property of the metal oxide layer is sufficiently ensured. When the thickness of the metal oxide layer is 50 nm or less, the transparency of the metal oxide layer and, by extension, the transparency of the laminated film and the packaging bag are ensured.

(A4) Barrier layer The material constituting the barrier layer is any one selected from the group consisting of a condensate of a metal alkoxide, a condensate of a hydrolysis product of a metal alkoxide, and a condensate of an alkoxysilylalkyl isocyanurate. Including one.

The metal alkoxide is, for example, an alkoxysilane such as a tetraalkoxysilane, an alkyltrialkoxysilane, or a dialkyldialkoxysilane. The alkoxy group is, for example, a methoxy group, an ethoxy group, or an ethoxymethoxy group. The alkoxysilylalkyl isocyanurate is, for example, 1,3,5-tris (3-trialkoxysilylalkyl) isocyanurate.

The barrier layer is, for example, a coating liquid obtained by mixing either one of metal alkoxide or a hydrolysis product of metal alkoxide, a polymer containing vinyl alcohol, an isocyanate compound, and a silane coupling agent. Formed using. Polymers containing vinyl alcohol are, for example, polyvinyl alcohol, polyvinyl acetate, and ethylene-vinyl acetate copolymers. The isocyanate compound is, for example, an aromatic isocyanate compound, a tolylene diisocyanate, and a xylylene diisocyanate.

Silane coupling agents are represented by the general formula R ³ Si (OR ⁴ ) ₃ . R ³ is an organic functional group, and OR ⁴ is a hydrolyzable alkoxy group such as a methoxy group, an ethoxy group, and an ethoxymethoxy group. The silane coupling agent is, for example, an epoxysilane coupling agent, an amine silane coupling agent, a vinylsilane coupling agent, and an acrylic silane coupling agent. A silane coupling agent having an isocyanate group may be used as a compound that also serves as both an isocyanate compound and a silane coupling agent.

When the barrier layer is analyzed using a time-of-flight secondary ion mass spectrometer (TOF-SIMS), a component derived from an alkoxysilane, a component derived from a polymer containing vinyl alcohol, and a component derived from an isocyanate compound. , And components derived from the silane coupling agent are detected. TOF-SIMS is a surface analysis method capable of measuring the mass spectrum of secondary ions generated when the surface of an analysis target is irradiated with ions and obtaining information on constituent elements and chemical structures on the surface of the analysis target. Is.

Clay minerals, stabilizers, colorants, viscosity modifiers, etc. are added to the barrier layer in consideration of adhesion to the layer adjacent to the barrier layer, wettability, and suppression of cracks due to shrinkage. Agents may be added. Clay minerals may be, for example, colloidal silica and smectite.

The thickness of the barrier layer is preferably 0.01 μm or more and 50 μm or less. When the thickness of the barrier layer is 0.01 μm or more, the gas barrier property of the barrier layer can be enhanced. When the barrier layer is 50 μm or less, cracks in the barrier layer can be suppressed.

One method of forming the barrier layer is to first mix a metal alkoxide or a hydrolysis product of the metal alkoxide, a polymer containing vinyl alcohol, an isocyanate compound, and a silane coupling agent in a solvent. This prepares the coating solution. Next, a coating liquid is applied to a base such as a metal oxide layer, and the coating film is dried to form a barrier layer. Since the metal alkoxide is difficult to disperse uniformly in an aqueous solvent, it is preferable to use a hydrolyzed metal alkoxide. As a method for forming the coating film and a method for drying the coating film, a method that can be used for forming the primer layer can be used.

(B) Water-based ink layer 12
The water-based ink layer 12 contains a colorant such as a pigment, a binder resin containing a polyurethane-based resin as a main component, and a water-based cross-linking agent. The side reaction between the water or water-based solvent remaining in the water-based ink layer 12 and the adhesive of the first solvent-free adhesive layer 13 causes bubbles between the gas barrier film layer 11 and the first solvent-free adhesive layer 13. It contributes to the occurrence. If the water-based ink layer 12 contains the polyurethane resin and the water-based cross-linking agent, a side reaction between the polyisocyanate component for forming the first solvent-free adhesive layer 13 and the component remaining in the water-based ink layer 12. As a result, the generation of air bubbles between the gas barrier film layer 11 and the first solvent-free adhesive layer 13 can be suppressed.

The polyurethane-based resin is a resin having a urethane bond and a derivative of a resin having a urethane bond. Polyurethane-based resins include polyurethane and polyurethane polyurea. Polyurethane is, for example, polyester polyurethane, polyether polyurethane, polyether polyester polyurethane, polycarbonate polyurethane, and a mixture thereof. Polyisocyanates for producing polyurethane-based resins are, for example, aliphatic isocyanates and aromatic isocyanates. Aliphatic isocyanates are, for example, methylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, and isopropylene diisocyanate. Aromatic isocyanates are, for example, phenylenediocyanates, 4,4-diphenylmethane diisocyanates, and naphthylene diisocyanates. Polyols for producing polyurethane-based resins are, for example, polyester polyols, polyether polyols, polycarbonate polyols, polycaprolactone polyols, and acrylic polyols.

The water-based ink layer 12 is formed by applying ink to the gas barrier film layer 11. The ink is produced by dissolving or dispersing a colorant, a binder resin, or the like in a solvent. The solvent constituting the ink is preferably an aqueous solvent containing water, and is, for example, at least one selected from an alcohol solvent, an ester solvent, and a ketone solvent. The alcohol solvent is, for example, methanol, ethanol, or isopropyl alcohol. The ester solvent is, for example, ethyl acetate or butyl acetate. The ketone solvent is, for example, methyl ethyl ketone.

From the viewpoint of reducing VOCs (Volatile Organic Compounds), the solvent constituting the ink is preferably an aqueous solvent, and the aqueous ink layer 12 is preferably a layer made of an aqueous ink. In addition, the amount of alcohol-based solvent remaining in the water-based ink layer 12 ^{is preferably 20 mg / m 2} or less. Further, the amount of water remaining in the water-based ink layer 12 ^{is preferably 100 mg / m 2} or less.

The ink contains a carbodiimide compound as an aqueous crosslinker. The carbodiimide compound is, for example, dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, diphenylcarbodiimide, dodecylisopropylcarbodiimide, benzylisopropylcarbodiimide. If the ink contains a carbodiimide-based compound, the water-based ink layer 12 can be easily made water-based. Further, since it is possible to reduce the amount of the alcohol-based solvent and the amount of water remaining in the water-based ink layer 12, it is possible to suppress the generation of bubbles and the generation of odor due to the residual solvent.

The printing methods for forming the water-based ink layer 12 are, for example, gravure printing and flexographic printing. The amount of ink applied when forming the water-based ink layer 12 is, for example, ^{preferably 0.5 g / m 2} or more and 15 g / m ² or less, and more preferably 1 g / m ² or more and 5 g / m ² or less. The water-based ink layers 12 are preferably scattered on the entire surface of the gas barrier film layer 11. That is, the water-based ink layer 12 is preferably located at a portion of the laminated film to be heat-welded.

(C) First solvent-free adhesive layer 13
The first solvent-free adhesive layer 13 is a cured product of a urethane-based solvent-free adhesive, and is formed from a urethane-based useless adhesive. The urethane-based solvent-free adhesive is a two-component curing type solvent-free adhesive that does not contain an organic solvent. The two-component curing type urethane-based useless adhesive contains a polyol component as a main agent and a polyisocyanate component as a curing agent. Hereinafter, the two-component curing type urethane-based solvent-free adhesive is also referred to as a solvent-free adhesive.

The polyol component is one selected from the group consisting of polyester polyols, polyether polyols, polyether ester polyols, and polyurethane polyols, or a mixture of two or more kinds, and the ends of the polyols are partially acid-modified. There is. The terminal hydroxyl group of the polyol component is partially acid-modified so that the valence is, for example, 2 or more and 20 or less. When the valence is 2 or more, the adhesive strength can be increased, and when the valence is 20 or less, the viscosity of the adhesive can be kept within an appropriate range for coating.

The polyester polyol is, for example, a polyvalent carboxylic acid, a dialkyl ester of the polyvalent carboxylic acid, and a transesterification product of a mixture thereof and a glycol-based solvent. Polycarboxylic acids are, for example, succinic acid, glutaric acid, isophthalic acid, terephthalic acid, adipic acid, pimelic acid, cork acid, azelaic acid, sebatic acid, dodecanedic acid, dimer acid. The glycol-based solvent is, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butylene glycol, neopentyl glycol, or 1,6-hexanediol.

The polyether polyol is, for example, a polymer of an oxylan compound and a low molecular weight polyol. Oxylan compounds are, for example, ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran. Low molecular weight polyols are water, ethylene glycol, propylene glycol, trimethylolpropane and glycerin.

The polyether ester polyol is obtained, for example, by reacting a polycarboxylic acid, a dialkyl ester of the polyvalent carboxylic acid, and a mixture thereof with a polyether polyol. The polyurethane polyol is, for example, a reaction product of a polyester polyol, a polyether polyol, a polyether ester polyol, and a polyisocyanate monomer.

The polyisocyanate component is a mixture of an aliphatic polyisocyanate and an aromatic polyisocyanate.
Aliphatic polyisocyanates are, for example, polyisocyanate monomers, polyisocyanate derivatives, and polyisocyanate-terminated prepolymers. The polyisocyanate monomer is, for example, tetramethylene diisocyanate, isopropylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, or trimethylhexamethylene diisocyanate. The polyisocyanate monomer is 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, lysine diisocyanate, and isophorone diisocyanate.

Aromatic polyisocyanates are, for example, polyisocyanate monomers, polyisocyanate derivatives, and polyisocyanate-terminated prepolymers. The polyisocyanate monomer is, for example, tolylene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate, or naphthalene diisocyanate. The polyisocyanate monomer is xylylene diisocyanate or tetramethylxylylene diisocyanate.

The polyisocyanate derivative is, for example, an isocyanurate compound derived from a polyisocyanate monomer. The polyisocyanate-terminated prepolymer is a bifunctional polyisocyanate containing a terminal isocyanate group obtained by reacting a polyisocyanate monomer with a bifunctional polyol compound such as polypropylene glycol. The polyisocyanate-terminated prepolymer is a polyisocyanate group-containing polyfunctional polyisocyanate obtained by reacting a polyisocyanate monomer with a trifunctional or higher functional polyol compound such as trimethylolpropane.

The coating amount of the first solvent-free adhesive layer 13 ^{is preferably 0.5 g / m 2} or more and 3.0 g / m ² or less, and more preferably 1.0 g / m ² or more and 2.0 g / m ² or less. When the coating amount of the first solvent-free adhesive layer 13 is 0.5 g / m ² or more, the delamination between the gas barrier film layer 11 and the intermediate base material layer 14 and the intermediate base material layer 14 The effect of suppressing delamination with the thermoplastic resin layer 16 can be enhanced. When the coating amount of the first solvent-free adhesive layer 13 is 3.0 g / m ² or less, it is possible to suppress the occurrence of winding misalignment during processing of the laminated film, and the appearance quality of the laminated film is good. In addition, proper lamination strength is obtained.

(D) Intermediate base material layer 14
The intermediate base material layer 14 has a single-layer structure made of one resin film or a laminated structure made of two or more resin films. The thickness of the intermediate base material layer 14 can be appropriately changed according to various resistances and processability required for the laminated film, and is, for example, 12 μm or more and 200 μm or less.

The material of the resin film constituting the intermediate base material layer 14 is, for example, a polyolefin resin, a polyamide resin, a polyester resin, a cyclic olefin resin, and a hydroxyl group-containing polymer. Polyolefin-based resins are, for example, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, and copolymers thereof, polyethylene, and polypropylene. The hydroxyl group-containing polymer is, for example, polyvinyl alcohol and an ethylene-vinyl alcohol copolymer. The material constituting the resin film is one of a polyolefin resin, a polyamide resin, a polyester resin, a cyclic olefin resin, and a hydroxyl group-containing polymer, or a combination of two or more.

The resin film constituting the intermediate base material layer 14 may be a stretched film or a non-stretched film. From the viewpoint of excellent mechanical strength and dimensional stability, the resin film is preferably a stretched film. The stretched film is a uniaxially stretched film or a biaxially stretched film.

(E) Second solvent-free adhesive layer 15
The second solvent-free adhesive layer 15 is a cured product of a urethane-based solvent-free adhesive, and is formed from a urethane-based useless adhesive. The urethane-based solvent-free adhesive contains a polyisocyanate component and a polyol component. The polyisocyanate component and the polyol component are selected from the materials exemplified as the urethane-based solvent-free adhesive for forming the second solvent-free adhesive layer 15. The solvent-free adhesive for forming the second solvent-free adhesive layer 15 and the solvent-free adhesive for forming the first solvent-free adhesive layer 13 may be the same or mutually. May be different.

(F) Thermoplastic resin layer 16
The thermoplastic resin layer 16 is a resin layer having heat-sealing properties. The thermoplastic resin is, for example, an ethylene resin, a polypropylene resin, a propylene resin, an ethylene-propylene copolymer, an ethylene-α, β unsaturated carboxylic acid copolymer, an ethylene-α, β unsaturated carboxylic acid copolymer. It is a coalesced esterified product. The ethylene-based resin is, for example, a high-density polyethylene, a linear low-density polyethylene, a low-density polyethylene, a medium-density polyethylene, or an ethylene-α-olefin copolymer. The polypropylene-based resin is, for example, homopolypropylene, block polypropylene, or random polypropylene. The propylene-based resin is, for example, a propylene-α-olefin copolymer. The ethylene-α and β unsaturated carboxylic acid copolymers are ethylene-acrylic acid copolymers and ethylene-methacrylic acid copolymers. The esterified product of the ethylene-α, β unsaturated carboxylic acid copolymer is, for example, methyl ethylene-acrylate, ethyl ethylene-acrylate, methyl ethylene-methyl methacrylate, and ethyl ethylene-ethyl methacrylate. The acid anhydride-modified polyolefin is, for example, a ternary copolymer such as an ethylene-maleic anhydride graft copolymer and an ethyl ethylene-ethyl acrylate-maleic anhydride.
The thickness of the thermoplastic resin layer 16 is, for example, 15 μm or more and 200 μm or less, and can be appropriately set according to the characteristics required for the laminated film.

(Packaging bag)
The packaging bag is formed by making a laminated film that heat-welds the thermoplastic resin layers 16 to each other. One method of manufacturing a packaging bag uses, for example, a single laminated film 50A having a rectangular shape, as shown in FIG. One laminated film 50A is folded in half so that the thermoplastic resin layers 16 in one laminated film 50A are in contact with each other. Next, the thermoplastic resin layers 16 on the left and right sides of the bent laminated film 50A are heat-welded to each other to produce a packaging bag having an opening. Then, the contents are filled into the inside of the packaging bag from the opening of the packaging bag, and the thermoplastic resin layers 16 located at the openings are heat-welded to each other, thereby providing one heat-welded portion 50Ah on three sides. The packaging bag is manufactured as a three-way pouch.

In another method of manufacturing a packaging bag, for example, the laminated film is bent into a tubular shape so that the thermoplastic resin layer 16 in one laminated film having a rectangular shape is on the inside. Then, the thermoplastic resin layers 16 located at the connection portion of the tubular surface are heat-welded to each other to form a backing portion, and the thermoplastic resin layers 16 located at the upper and lower openings of the tubular surface are heat-welded to each other. As a result, a packaging bag having a pillow shape with a heat-welded portion is manufactured.

In addition, another method for producing a packaging bag uses, for example, two laminated films having a rectangular shape. The two laminated films are laminated so that the thermoplastic resin layers 16 located on the four sides of the two laminated films are in contact with each other. Then, the thermoplastic resin layers 16 located on the four sides are heat-welded to each other to manufacture one packaging bag having heat-welded portions on all sides.

(Production method)
In the method for producing a laminated film, first, a water-based ink layer 12 is formed on the barrier layer of the gas barrier film layer 11. The surface on which the water-based ink layer 12 is formed is an example of the first surface of the gas barrier film layer 11. Next, a two-component curable solvent-free adhesive for forming the first solvent-free adhesive layer 13 is applied to the gas barrier film layer 11 by using a roll coating method or the like, and the first solvent-free adhesive layer 13 is applied. The gas barrier film layer 11 and the first surface of the intermediate base material layer 14 are bonded to each other.

Next, a two-component curable solvent-free adhesive for forming the second solvent-free adhesive layer 15 is applied to the second surface of the intermediate base material layer 14 by a roll coating method or the like, and the intermediate base material layer is applied. A second solvent-free adhesive layer 15 is formed on the second surface of 14. Then, the second surface of the intermediate base material layer 14 and the thermoplastic resin layer 16 are joined via the second solvent-free adhesive layer 15.

As shown in FIG. 3, when the first solvent-free adhesive layer 13 is formed by the roll coating method, the solvent-free adhesive 13B is accumulated between the doctor roll Y1 and the application roll Y2. The solvent-free adhesive accumulated between the rolls is heated and mixed, and is transferred from the doctor roll Y1 to the coating roll Y4 through the metering roll Y3. The solvent-free adhesive 13B transferred to the coating roll Y4 is applied to the gas barrier film layer 11 sent between the coating roll Y4 and the packing roll Y5.

At this time, the solvent-free adhesive 13B coated on the gas barrier film layer 11 is peeled off from the coating roll Y4 at the subsequent stage of the coating roll Y4. The residue 13B1 of the solvent-free adhesive peeled off from the coating roll Y4 causes a stringing phenomenon such as stretching a thread between the gas barrier film layer 11 and the coating roll Y4. The stringing phenomenon due to the residue 13B1 causes fine irregularities on the surface of the gas barrier film layer 11 due to the solvent-free adhesive 13B. The unevenness of the solvent-free adhesive 13B containing no organic solvent is not smoothed in the subsequent stage of the coating roll Y4, and bubbles are generated between the gas barrier film layer 11 and the intermediate base material layer 14. It becomes a cause.

Therefore, when the first solvent-free adhesive layer 13 is formed by using the roll coating method, the coating temperature of the solvent-free adhesive 13B, that is, the temperature of the coating roll Y4 can be set as follows. preferable. That is, the temperature of the coating roll Y4 can be set so that the cone / plate viscosity according to JIS K 5600-2-2: 2014 after 45 minutes from mixing is 3500 mPa · s or more and 6000 mPa · s or less. preferable.

Further, from the viewpoint of further improving the smoothness of the solvent-free adhesive, it is preferable to set the transfer temperature of the doctor roll Y1 as follows. That is, the temperature of the doctor roll Y1 can be set so that the cone / plate viscosity according to JIS K 5600-2-2: 2014 after 45 minutes from mixing is 2500 mPa · s or more and 3500 mPa · s or less. preferable.

FIG. 4 shows an example of the relationship between the cone-plate viscosity of the solvent-free adhesive 13B and the elapsed time from mixing. In FIG. 4, xylylene diisocyanate (XDI) and hexamethylene diisocyanate (HDI) (trade name "TSN-4864B-3": manufactured by Toyo Morton Co., Ltd.) are used as polyisocyanate components, and polyester polyol is used as a polyol component. This is an example using (trade name "TSN-4864A": manufactured by Toyo Morton Co., Ltd.). The blending ratio of XDI and HDI is 100: 100.

As shown in FIG. 4, the cone-plate viscosity of the two-component curable urethane-based solvent-free adhesive shows a lower value immediately after mixing as the temperature of the solvent-free adhesive increases. For example, the viscosity of a cone plate at a level where the temperature of the solvent-free adhesive is 80 ° C. is lower than the level at which the temperature is 70 ° C., and the cone plate at a level where the temperature of the solvent-free adhesive is 90 ° C. The viscosity is lower than the level of 80 ° C., and at any level, the cone plate viscosity is 1000 mPa or less.

On the other hand, the degree of increase in the viscosity of the cone plate with respect to the unit elapsed time tends to increase as the temperature of the solvent-free adhesive increases immediately after mixing. For example, the degree of increase in the level at which the temperature of the solvent-free adhesive is 80 ° C. is higher than the level at which the temperature is 70 ° C., and the degree of increase in the level at which the temperature of the solvent-free adhesive is 90 ° C. is 80. Higher than the level at ℃. In addition, the degree of increase in the level at which the temperature of the solvent-free adhesive is 90 ° C. is significantly higher than the level at which the temperature is 70 ° C. or 80 ° C. The cone-plate viscosity at a level where the temperature of the solvent-free adhesive is 70 ° C. or higher and 80 ° C. or lower is 2500 mPa · s or more and 3500 mPa · s when 45 minutes have passed from the mixing. On the other hand, the viscosity of the cone / plate at a level where the temperature of the solvent-free adhesive is 90 ° C. becomes 3500 mPa · s or more and 6000 mPa · s or less when 45 minutes have passed from the mixing.

As described above, the stringing phenomenon due to the residue 13B1 contributes to the generation of air bubbles between the gas barrier film layer 11 and the intermediate base material layer 14. Raising the temperature of the coating roll Y4 to raise the coating temperature of the solvent-free adhesive 13B suppresses the stringing phenomenon due to the residue 13B1, so that the coating temperature of the solvent-free adhesive 13B is preferably high. .. On the other hand, the high temperature of the solvent-free adhesive 13B increases the degree of increase in the viscosity of the cone plate over a unit elapsed time and shortens the pot life, which is the pot life. In this regard, as described above, if the cone-plate viscosity after 45 minutes from mixing is 3500 mPa · s or more, the stringing phenomenon due to the residual 13B1 can be suppressed, and it should be 6000 mPa · s or less. For example, it is possible to suppress the shortening of the pot life of the solvent-free adhesive 13B.

These preferred settings are the same when the second solvent-free adhesive layer 15 is formed by using the roll coating method.
[Second layer configuration]
The layer structure of the laminated film can be changed to the second layer structure. The second layer structure is a structure in which the primer layer is omitted from the first layer structure, and the layer structure of the gas barrier film layer 11 is mainly different. The gas barrier film layer 11 has a layer structure described as (A1) base film layer / (A3) metal oxide layer / (A4) barrier layer. That is, the gas barrier film layer 11 includes a base film layer, a metal oxide layer, and a barrier layer. The metal oxide layer is located between the base film layer and the barrier layer. The barrier layer is located between the base film layer and the first solvent-free adhesive layer 13.

The substrate film layer comprises a plasma treated surface. The metal oxide layer is in contact with the surface of the base film layer. The barrier layer is in contact with the surface of the metal oxide layer opposite to the surface in contact with the base film layer.

The base film layer is the same as the base film layer described in the first layer structure, except that it includes a plasma-treated surface. The plasma treatment is, for example, reactive ion etching and is performed using a hollow anode plasma processing apparatus provided with an anode facing the surface. The plasma-treated surface is enhanced with various adhesion functions such as a chemical adsorption function and an anchor function to enhance the adhesion between the surface and the metal oxide layer.

[Third layer configuration]
The layer structure of the laminated film can be changed to a third layer structure. The second layer structure is a structure in which the primer layer and the metal oxide layer are omitted from the first layer structure, and the layer structure of the gas barrier film layer 11 is mainly different. The gas barrier film layer 11 has a layer structure described as (A1) base film layer / (A4) barrier layer. That is, the gas barrier film layer 11 includes a base film layer and a barrier layer. The barrier layer is in contact with the base film layer and the first solvent-free adhesive layer 13.

The material constituting the barrier layer is a dried product of a coating film containing a water-soluble polymer having a hydroxyl group. A water-soluble polymer is a polymer that can be completely dissolved or finely dispersed in water at room temperature. The material constituting the barrier layer includes, for example, a polycarboxylic acid-based polymer. A polycarboxylic acid-based polymer is a polymer having two or more carboxy groups in one molecule. The polycarboxylic acid-based polymer is, for example, a homopolymer of α, β-monoethylene unsaturated carboxylic acid, a copolymer of two or more kinds of α, β-monoethyl unsaturated carboxylic acid, α, β-. It is a copolymer of a monoethylenically unsaturated carboxylic acid and another ethylenically unsaturated monomer. Further, the polycarboxylic acid-based polymer is an acidic polysaccharide having a carboxyl group in the molecule, such as alginic acid, carboxymethyl cellulose, and pectin. As the polycarboxylic acid-based polymer constituting the barrier layer, one selected from the above can be used alone or in combination of two or more.

The α, β-monoethylene unsaturated carboxylic acids are, for example, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid. Other ethylenically unsaturated monomers that can be copolymerized with α, β-monoethylenically unsaturated carboxylic acids include, for example, saturated carboxylic acid vinyl esters, alkyl acrylates, alkyl methacrylates, alkyl itacones, acrylonitrile, vinyl chloride, etc. Vinylidene chloride, vinyl fluoride, vinylidene fluoride, and styrene. Saturated carboxylic acid vinyl esters are, for example, ethylene, propylene, and vinyl acetate.

When the polycarboxylic acid-based polymer is a polymer formed only from α, β-monoethylene unsaturated carboxylic acid, the polymer is acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid. , And at least one polymerizable monomer selected from the group composed of crotonic acid can be polymerized to obtain a carboxylic acid-based polymer. The polymer is preferably a polymer obtained by polymerizing at least one polymerizable monomer selected from the group composed of acrylic acid, methacrylic acid, and maleic acid. Further, the polymer is more preferably polyacrylic acid, polymethacrylic acid, and polymaleic acid, or a mixture thereof.

The barrier layer may contain other polymers in addition to the polycarboxylic acid-based polymer as long as the gas barrier property is not impaired. The barrier layer may be formed from, for example, a mixture of a polycarboxylic acid-based polymer and a polyalcohol.

The polyalcohol is a compound containing two or more hydroxyl groups in the molecule, and may be a low molecular weight compound or an alcohol-based polymer. The polyalcohol may be, for example, polyvinyl alcohol, sugars, starch and the like. The low molecular weight compounds described above are, for example, glycerin, ethylene glycol, propylene glycol, 1,3-propanediol, pentaerythritol, polyethylene glycol, and polypropylene glycol. As the polyalcohol contained in the barrier layer, one selected from the above can be used alone or in combination of two or more.

The saponification degree of polyvinyl alcohol is preferably 95% or more, and more preferably 99% or more. The average degree of polymerization of polyvinyl alcohol is preferably 300 or more and 1500 or less. The polyalcohol is preferably a vinyl alcohol poly (meth) acrylic acid copolymer containing vinyl alcohol as a main component. A vinyl alcohol poly (meth) acrylic acid copolymer containing vinyl alcohol as a main component is preferable in that it has compatibility with a polycarboxylic acid-based polymer.

The saccharides may be monosaccharides, oligosaccharides, and polysaccharides. Sugars include sugar alcohols, sugar alcohol substitutions, and derivatives of sugar alcohols. Sugar alcohols include, for example, sorbitol, mannitole, zulcitol, xylitol, and erythritol. The sugar is preferably water, alcohol, or a sugar that dissolves in a mixed solution of water and alcohol. As the saccharide contained in the barrier layer, one selected from the above can be used alone or in combination of two or more.

Starches are included in polysaccharides. Starches are, for example, raw starch, i.e. undenatured starch, or various modified starches. Raw starch is, for example, wheat starch, corn starch, potato starch, tapioca starch, rice starch, sweet potato starch, and sago starch. Modified starches are, for example, physically modified starches, enzyme-modified starches, chemically modified starches, and grafted starches obtained by graft-polymerizing a monomer on starches. Among the starches, water-soluble processed starch obtained by hydrolyzing potato starch with an acid or sugar alcohol in which the aldehyde group which is the terminal group of the starch is substituted with a hydroxyl group is preferable. The starches may be hydrous. As the starches contained in the barrier layer, one selected from the above can be used alone or in combination of two or more.

One method of forming the barrier layer is first, first, a first coating liquid containing a polycarboxylic acid-based polymer and a solvent, or a second coating solution containing a polycarboxylic acid-based polymer, polyalcohol, and a solvent. The liquid is applied onto the base film layer. Next, the solvent is evaporated by drying the first coating liquid or the second coating liquid to form a barrier layer.

The first coating liquid is prepared by dissolving or dispersing a polycarboxylic acid-based polymer in a solvent. The solvent may be any liquid that can uniformly dissolve or disperse the polycarboxylic acid polymer. The solvent may be, for example, water, methyl alcohol, ethyl alcohol, isopropyl alcohol, dimethylsulfoxide, dimethylformamide, dimethylacetamide and the like.

The second coating liquid is, for example, a method of dissolving each component other than the solvent constituting the second coating liquid in a solvent, a method of mixing a solution containing each component, and a method of mixing a carboxyl group in a solution of polyalcohol. It is prepared by a method of polymerizing the containing monomer and, if necessary, neutralizing the solution with an alkali after the polymerization.

The first coating liquid and the second coating liquid are other polymers, softeners, plasticizers, and stabilizers as long as the barrier property of oxygen gas in the barrier layer formed by using them is not impaired. , Anti-blocking agents, pressure-sensitive adhesives, and inorganic layered compounds and the like may be included. The plasticizer excludes low molecular weight compounds having two or more hydroxyl groups in the molecule. The inorganic superficial compound is, for example, montmorillonite.

The first coating liquid may contain a monovalent metal and a compound containing at least one of the divalent metals. Thereby, the barrier property of oxygen gas in the barrier layer can be enhanced. The monovalent and divalent metals are, for example, sodium, potassium, zinc, calcium, magnesium, and copper. Compounds containing at least one of the monovalent metal and the divalent metal are, for example, sodium hydroxide, zinc oxide, calcium hydroxide, and calcium oxide.

For the purpose of improving the oxygen gas barrier property, the base film layer may be coated with the second coating liquid, and the coating film may be dried and then heat-treated. At this time, for the purpose of relaxing the heat treatment conditions, when preparing the second coating liquid, an alkali metal compound, or an alkali metal salt of an inorganic acid or an organic acid, which is soluble in water, is used as the second coating liquid. It may be added. The alkali metal compound is, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide. Alkali metal salts of inorganic and organic acids include, for example, lithium chloride, sodium chloride, potassium chloride, sodium bromide, sodium phosphinate (sodium hypophosphite), disodium hydrogen phosphite, disodium phosphate, ascorbin. Sodium acid, sodium acetate, sodium benzoate, sodium hyposulfate. Among these alkali metal salts, phosphinic acid metal salts such as sodium phosphinate and calcium phosphinate are preferable.

For the method of forming the coating film using the first coating liquid and the second coating liquid and the method of drying the coating film, a method that can be used for forming the primer layer is used. Can be done.
Another method of forming the barrier layer is to apply a coating liquid containing a monomer for forming a polycarboxylic acid-based polymer onto the base film layer. Then, the coating liquid is irradiated with ultraviolet rays or electron beams to polymerize the monomers to form a barrier layer.

In another method of forming the barrier layer, a monomer forming a polycarboxylic acid-based polymer is vapor-deposited on the base film layer, and the vapor-deposited monomer is irradiated with an electron beam to polymerize the monomer to polymerize the barrier layer. To form.

The thickness of the barrier layer is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 1 μm or less. The barrier layer may be provided with a coating layer containing a zinc compound on the surface in contact with the first solvent-free adhesive layer 13.

Zinc compounds are, for example, zinc oxides, hydroxides, carbonates, organic acid salts, and inorganic acid salts. The zinc compound is preferably zinc oxide, zinc hydroxide, zinc carbonate, zinc acetate, or zinc phosphate. The toxicity of zinc is low, and the white zinc sulfide produced by the reaction of hydrogen sulfide, which causes the retort odor, with zinc has almost no effect on the appearance of the packaging bag.

From the viewpoint of coating suitability and dispersibility in a solvent, the zinc compound is preferably in the form of particles having an average particle size of 5 μm or less, more preferably 1 μm or less, and further preferably 0.1 μm or less. preferable. As the content of the zinc compound increases, the flavor of the contents may be impaired. For example, when the content is a food having an important flavor derived from a sulfur-containing compound, such as a garlic seasoning product, the flavor of the food is likely to be impaired. Therefore, it is preferable that the content of the zinc compound is appropriately changed depending on the contents of the packaging bag.

The thickness of the coating layer is preferably 0.1 μm or more and 10 μm or less, more preferably 0.1 μm or more and 2 μm or less, and further preferably 0.1 μm or more and 1 μm or less. When the thickness of the coating layer is 0.1 μm or more, the thickness of the coating layer is likely to be stable. When the thickness of the coating layer is 10 μm or less, the coating layer is less likely to coagulate and fracture.

The method of forming the coating layer is, for example, applying a solvent or a coating agent containing a dispersion medium and a zinc compound. The solvent or dispersion medium is, for example, water, methyl alcohol, ethyl alcohol, isopropyl alcohol, dimethyl sulfoxide, dimethyl formamide, toluene, hexane, acetone, methyl ethyl ketone, diethyl ether, dioxane, tetrahydrofuran, ethyl acetate, butyl acetate. Is.

The coating agent may appropriately contain additives such as a resin, a surfactant, a softening agent, a stabilizer, a film forming agent, an antiblocking agent, and an adhesive. The resin is, for example, a paint resin such as an alkyd resin, a melamine resin, an acrylic resin, a nitrified cotton, a urethane resin, a polyester resin, a phenol resin, an amino resin, a fluororesin, or an epoxy resin. From the viewpoint of dispersibility of the zinc compound, the coating agent preferably contains a dispersant.
As a method for forming a coating layer using a coating agent, a method that can be used for forming a primer layer can be used.

[4th layer configuration]
The layer structure of the laminated film can be changed to the fourth layer structure. The fourth layer structure is a structure in which the primer layer and the metal oxide layer are omitted from the first layer structure, and the layer structure of the gas barrier film layer 11 is mainly different. The gas barrier film layer 11 has a layer structure described as (A1) base film layer / (A4) barrier layer. That is, the gas barrier film layer 11 includes a base film layer and a barrier layer. The barrier layer is in contact with the base film layer and the first solvent-free adhesive layer 13.

The barrier layer contains a hydrolysis product of a metal oxide and a phosphorus compound. The hydrolysis product of the metal oxide and the phosphorus compound enhances the adhesion between the base film layer and the barrier layer and suppresses the occurrence of delamination between the base film layer and the barrier layer.

The barrier layer is a single layer containing a hydrolysis product of a metal oxide and a phosphorus compound, or a multilayer layer containing a hydrolysis product.
The metal atoms constituting the metal oxide are, for example, Mg, Ca, Zn, Al, Si, Ti, and Zr, and have a valence of divalent or higher. A metal oxide is produced by hydrolyzing and condensing a metal compound having a hydrolyzable functional group. The method of hydrolyzing and condensing a metal compound is a liquid phase synthesis method such as a sol-gel method. The metal oxide is a fine particle and has, for example, a spherical shape, a flat shape, a polyhedral shape, a fibrous shape, and a needle shape. From the viewpoint of enhancing the barrier property and heat resistance and water resistance, the metal oxide particles are preferably fibrous or needle-like. The average particle size of the metal oxide particles is, for example, 1 nm or more and 0.5 μm or less. From the viewpoint of excellent barrier properties and transparency of the barrier layer, the average particle size of the metal oxide is preferably 1 nm or more and 100 nm or less.

Phosphorus compounds are, for example, phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, and derivatives thereof. Phosphorus compounds have one or more reaction points that react with metal oxides. The reaction point is a bond between a phosphorus atom and an oxygen atom, or a bond between a phosphorus atom and a halogen atom.

The hydrolysis product of the metal oxide and the phosphorus compound has a structure in which particles of the metal oxide are bonded to each other via a phosphorus atom derived from the phosphorus compound. The hydrolysis product of the metal oxide and the phosphorus compound is obtained, for example, by heat-treating the coating film containing the metal oxide and the phosphorus compound.

The barrier layer may contain polyvinyl alcohol, a partially saponified product of polyvinyl acetate, polyethylene glycol, polyhydroxyethyl (meth) acrylate, polysaccharides such as starch, and polysaccharide derivatives derived from polysaccharides. The barrier layer may also contain polyacrylic acid, polymethacrylic acid, (poly) acrylic acid / methacrylic acid, and salts thereof. The barrier layer includes ethylene-vinyl alcohol copolymer, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer, ethylene-acrylic acid copolymer, and the like. It may contain a saponified product of an ethylene-ethyl acrylate copolymer.

From the viewpoint of obtaining high barrier properties and high heat resistance, the maximum absorbed wavenumber in the infrared absorption spectrum in the range of ^{800 cm -1} or more and 1400 cm ^{-1 or less in the barrier layer is within the range of 1080 cm -1} or more and 1130 cm ^-1 or less. Is preferable. Since the maximum absorbed wavenumber is in ^{the range of 1080 cm -1} or more and 1130 cm ^-1 or less, the metal atom is preferably Al.

From the viewpoint of suppressing the dimensional change of the gas barrier film layer from changing during printing or laminating, the upper limit of the thickness of the barrier layer is preferably 4.0 μm, more preferably 2.0 μm, and further 1.0 μm. Preferably, 0.9 μm is particularly preferable. Further, the thinner the barrier layer, the more flexible the gas barrier film layer is, and the mechanical properties of the gas barrier film layer can be brought closer to the mechanical properties of the base film layer itself. The lower limit of the thickness of the barrier layer is preferably 0.1 μm, more preferably 0.2 μm.

[Example 1]
A first layer structure is used as the layer structure of the gas barrier film layer 11, and a biaxially stretched nylon film (trade name "ONMB-RT": manufactured by Unitika Ltd.) having a thickness of 15 μm is used as the intermediate base material layer 14. Using. Further, as the thermoplastic resin layer 16, a non-stretched polypropylene film (trade name “ZK500”: manufactured by Toray Film Processing Co., Ltd.) having a thickness of 70 μm for retort sterilization was used. Further, as the ink, a water-based ink (manufactured by Toyo Ink Co., Ltd.) containing a polyurethane resin and a carbodiimide compound which is an water-based cross-linking agent was used.

As a solvent-free adhesive for forming the first solvent-free adhesive layer 13, a two-component curable urethane-based solvent-free adhesive was used. At this time, a polyisocyanate component (trade name "TSN-4864B-3": manufactured by Toyo Morton Co., Ltd.) containing XDI as an aromatic polyisocyanate and containing HDI as an aliphatic polyisocyanate was used. Further, as a polyol component, a polyester polyol (trade name "TSN-4864A": manufactured by Toyo Morton Co., Ltd.) was used. The compounding ratio of the polyisocyanate component and the polyol component is 100: 100.

As a solvent-free adhesive for forming the second solvent-free adhesive layer 15, a two-component curable urethane-based solvent-free adhesive was used. At this time, a polyisocyanate component (trade name "TSN-4864B-3": manufactured by Toyo Morton Co., Ltd.) containing XDI as an aromatic polyisocyanate and containing HDI as an aliphatic polyisocyanate was used. Further, as a polyol component, a polyester polyol (trade name "TSN-4864A": manufactured by Toyo Morton Co., Ltd.) was used. The compounding ratio of the polyisocyanate component and the polyol component is 100: 100.

First, a water-based ink layer 12 was formed on the barrier layer of the gas barrier film layer by using a flexographic printing method so that the coating amount was 1.4 g / m ^2. The amount of water remaining in the water-based ink layer 12 was 13 mg / m ² . The amount of alcohol solvent remaining in the water-based ink layer 12 was 1.5 mg / m ² .

Next, using a non-solvent laminating method using a solvent-free adhesive, the water-based ink layer 12 and the barrier layer other than the water-based ink layer 12 are covered so ^{that the coating amount is 1.8 g / m 2.} , The first solvent-free adhesive layer 13 was formed. Then, the gas barrier film layer 11 and the first surface of the biaxially stretched nylon film were bonded to each other via the first solvent-free adhesive layer 13.

Next, a second solvent-free adhesive layer was applied to the second surface of the biaxially stretched nylon film by using a non-solvent laminating method using a solvent-free adhesive so that the coating amount was 1.8 g / m ^2. 15 was formed. Subsequently, one surface of the unstretched polypropylene film was subjected to a corona discharge treatment, and the treated surface of the unstretched polypropylene film and the second solvent-free adhesive layer 15 were bonded together.

At this time, in forming the first solvent-free adhesive layer 13, the processing speed, which is the transport speed of the gas barrier film layer 11, was set to 150 m / min. Further, the temperature of the doctor roll Y1 (first roll) was set to 70 ° C., and the temperature of the solvent-free adhesive between the doctor roll Y1 and the application roll Y2 was set to 70 ° C. Then, the temperature of the coating roll Y4 (second roll) was set to 80 ° C. Similarly, in the formation of the second solvent-free adhesive layer 15, the temperature of the solvent-free adhesive was set to 70 ° C., the temperature of the first roll was set to 70 ° C., and the temperature of the second roll was set to 80 ° C.

That is, the transfer temperature of the first roll and the temperature of the solvent-free adhesive were set so that the cone-plate viscosity after 45 minutes from mixing was 2500 mPa · s or more and 3500 mPa · s or less. Further, the coating temperature of the second roll was set so that the cone plate viscosity after 45 minutes from the mixing was 2500 mPa · s or more and 3500 mPa · s or less. As a result, the laminated film of Example 1 was obtained.

[Example 2]
In the formation of the first solvent-free adhesive layer 13 and the formation of the second solvent-free adhesive layer 15, the processing speed, which is the transport speed of the gas barrier film layer 11, is set to 200 m / min, and other conditions are implemented. The laminated film of Example 2 was obtained in the same manner as in Example 1.

[Example 3]
In the formation of the first solvent-free adhesive layer 13, the processing speed, which is the transport speed of the gas barrier film layer 11, was set to 200 m / min. Further, the temperature of the doctor roll Y1 (first roll) was set to 80 ° C., and the temperature of the solvent-free adhesive between the doctor roll Y1 and the application roll Y2 was set to 80 ° C. Then, the temperature of the coating roll Y4 (second roll) was set to 90 ° C. Similarly, in the formation of the second solvent-free adhesive layer 15, the temperature of the solvent-free adhesive was set to 80 ° C., the temperature of the first roll was set to 80 ° C., and the temperature of the second roll was set to 90 ° C.

That is, the transfer temperature of the first roll and the temperature of the solvent-free adhesive were set so that the cone-plate viscosity after 45 minutes from mixing was 2500 mPa · s or more and 3500 mPa · s or less. Further, the coating temperature of the second roll was set so that the cone plate viscosity after 45 minutes from the mixing was 3500 mPa · s or more and 6000 mPa · s or less. As a result, the laminated film of Example 3 was obtained.

[Comparative Example 1]
As the ink, a water-based ink containing a polyurethane resin and not containing a water-based cross-linking agent was used. Further, as a solvent-free adhesive for forming the first solvent-free adhesive layer 13, a two-component curable urethane-based solvent-free adhesive was used. At this time, as the aromatic polyisocyanate, a polyisocyanate component (trade name "2K-SF-900A": manufactured by DIC Corporation) containing only XDI was used. Further, as a polyol component, a polyester polyol (trade name "2-HA-700B": manufactured by DIC Corporation) was used.
The blending ratio of the polyisocyanate component and the polyol component is 100: 200.

[Qualitative evaluation]
Curing was performed for 72 hours at a curing temperature of 50 ° C. using the laminated films of Examples 1 to 3, and 3 m was cut off from the outside of the wound body of the laminated film after curing to form the residue of the wound body. As the qualitative appearance of the film, the appearance of the residue was visually observed. Table 1 shows the results of the qualitative appearance of each of the laminated films of Examples 1 to 3.
In the qualitative appearance of Table 1, “⊚” marks indicate that no bubbles were observed by visual observation. The “◯” mark indicates that bubbles were observed by visual observation seen from the thermoplastic resin layer 16, but no bubbles were observed by visual observation seen from the gas barrier film layer 11. The “Δ” mark indicates that bubbles are observed at both the visual observation seen from the thermoplastic resin layer 16 and the visual observation seen from the gas barrier film layer 11.

As shown in Table 1, the best appearance was observed in Example 3 in which the temperature of the first roll was set to 80 ° C. and the temperature of the second roll was set to 90 ° C. Further, even in Example 1 in which the temperature of the first roll is set to 70 ° C. and the temperature of the second roll is set to 80 ° C., if the method is to reduce the processing speed to 150 m / min, the gas barrier film layer 11 can be used. A good appearance was observed by visual observation. Further, even in Example 2 in which the temperature of the first roll is set to 70 ° C., the temperature of the second roll is set to 80 ° C., and the processing speed is increased to 200 m / min, the laminated film of Comparative Example 1 is used. Compared with, a good appearance was observed. In the laminated film of Comparative Example 1, in both the visual observation seen from the thermoplastic resin layer 16 and the visual observation seen from the gas barrier film layer 11, a speckled shape composed of a large number of bubbles as compared with Example 2. The appearance of was recognized.

[Quantitative evaluation]
Curing was performed for 72 hours at a curing temperature of 50 ° C. using the laminated films of Examples 1 to 3, and a microscope (trade name "VHX-6000") was applied to the transparent portion other than the ink layer 12 in the cured laminated film. : Microscopic observation was performed using (manufactured by KEYENCE CORPORATION). At this time, the observation magnification is set to 50 times, the image is taken from the gas barrier film layer 11, and the image obtained by the observation is binarized to determine the area of the bubble portion in the total area of the observation image. The ratio was measured as a result of quantitative observation.

Table 1 shows the results of the quantitative appearance of each of the laminated films of Examples 1 to 3. Further, a binarized image obtained from the laminated film of Example 3 is shown in FIG. 5, and a binarized image obtained from the laminated film of Example 1 is shown in FIG.

In the quantitative observation of Example 3, the area ratio of the bubble portion is 0.3%, which is 1.4% which is the area ratio of Example 2, and further, 0.9% which is the area ratio of Example 1. It was found to be much lower than. Further, from the comparison between FIGS. 5 and 6, the laminated film of Example 1 contains relatively large bubbles having a diameter of 100 μm to 500 μm, while the laminated film of Example 3 has a diameter of 100 μm to 200 μm. It was found to contain only small bubbles up to.

[Taste evaluation]
A three-way pouch was prepared using the laminated films of Examples 1 to 3, and the prepared three-way pouch was filled with 150 ml of water. Then, using a three-way pouch sealed with water, heat treatment was performed at a treatment temperature of 130 ° C. for 110 minutes, and taste sensory evaluation was performed after 24 hours.

In the taste sensory evaluation of Example 3, a taste superior to that of Comparative Example 1 was observed, while in the taste evaluation of Examples 1 and 2, it was confirmed to be comparable to that of Comparative Example 1.

As described above, according to the above embodiment, the following effects can be obtained.
(1) Since the first solvent-free adhesive layer 13 and the second solvent-free adhesive layer 15 are formed by using a two-component curable urethane-based solvent-free adhesive, a packaging material for retort heat sterilization or the like is formed. It is possible to improve the environmental compatibility even with the laminated film used in the above.

(2) Since the water-based ink layer 12 contains the polyurethane resin and the water-based cross-linking agent, the water and solvent components remaining in the water-based ink layer 12 and the adhesive for forming the first solvent-free adhesive layer 13 are secondary. The reaction, and by extension, the generation of air bubbles between the gas barrier film layer 11 and the first solvent-free adhesive layer 13 can be suppressed.

(3) Since the polyisocyanate component constituting the first solvent-free adhesive layer 13 and the second solvent-free adhesive layer 15 is a mixture of an aliphatic polyisocyanate and an aromatic polyisocyanate, it is laminated. It is possible to prevent the film from exhibiting a speckled appearance.

(4) When the amount of alcohol solvent remaining in the water-based ink layer 12 is 20 mg / m ² or less and the amount of water remaining in the water-based ink layer 12 is 100 mg / m ² or less, the gas barrier film layer 11 and the first 1 The effectiveness of the effect of suppressing the formation of air bubbles with the solvent-free adhesive layer 13 can be enhanced.

(5) Any method in which the temperature of the coating roll Y4 is set so that the cone / plate viscosity becomes 3500 mPa · s or more when 45 minutes have passed from the mixing of the two-component curable urethane-based solventless adhesive. For example, the adhesive can be smoothed to the extent that deterioration of the appearance quality of the laminated film can be sufficiently suppressed.

(6) Any method in which the temperature of the coating roll Y4 is set so that the cone / plate viscosity becomes 6000 mPa · s or less when 45 minutes have passed from the mixing of the two-component curing type urethane solvent-free adhesive. For example, it is possible to prevent the pot life, which is the pot life, from becoming excessively short.

11 ... Gas barrier film layer, 12 ... Water-based ink layer, 13 ... First solvent-free adhesive layer, 14 ... Intermediate base material layer, 15 ... Second solvent-free adhesive layer, 16 ... Thermoplastic resin layer, 50A ... Laminated film ..

Claims (13)

Gas barrier film layer and
With a thermoplastic resin layer,
An intermediate base material layer located between the gas barrier film layer and the thermoplastic resin layer,
A first solvent-free adhesive layer located between the gas barrier film layer and the intermediate base material layer,
A second solvent-free adhesive layer located between the intermediate base material layer and the thermoplastic resin layer,
A water-based ink layer located between the gas barrier film layer and the first solvent-free adhesive layer is provided.
The water-based ink layer contains a polyurethane-based resin and a water-based cross-linking agent.
The adhesive forming each adhesive layer is a two-component curable urethane-based solventless adhesive containing a partially acid-modified polyol component and a polyisocyanate component.
The polyisocyanate component is a laminated film which is a mixture of an aliphatic polyisocyanate and an aromatic polyisocyanate. The aqueous cross-linking agent is a carbodiimide compound and
The polyol component is a polyester polyol,
The aliphatic polyisocyanate is hexamethylene diisocyanate.
The laminated film according to claim 1, wherein the aromatic polyisocyanate is xylylene diisocyanate. The laminated film according to claim 2, wherein the amount of the alcohol solvent remaining in the water-based ink layer is 20 mg / m ^{2 or less.} The laminated film according to claim 2 or 3, wherein the amount of water remaining in the water-based ink layer is 100 mg / m ^{2 or less.} The gas barrier film layer is
Base film layer and
A barrier layer located between the base film layer and the first solvent-free adhesive layer,
A primer layer located between the base film layer and the barrier layer,
A metal oxide layer located between the primer layer and the barrier layer is provided.
The material constituting the barrier layer is a condensate of a metal alkoxide, a condensate of a hydrolysis product of a metal alkoxide, a condensate of alkoxysilylalkyl isocyanurate, and a coating film of a water-soluble polymer having a hydroxyl group. The laminated film according to any one of claims 1 to 4, which comprises any one selected from the group consisting of dried products. The gas barrier film layer is
Base film layer and
A barrier layer located between the base film layer and the first solvent-free adhesive layer,
A primer layer located between the base film layer and the barrier layer,
A metal oxide layer located between the primer layer and the barrier layer is provided.
The primer layer according to any one of claims 1 to 4, wherein the primer layer contains a reaction product of any one of a trialkoxysilane and a hydrolysis product of a trialkoxysilane, an acrylic polyol, and an isocyanate compound. Laminated film. The gas barrier film layer is
Base film layer and
Any one of claims 1 to 4, which is a barrier layer located between the base film layer and the first solvent-free adhesive layer and includes the barrier layer containing a polycarboxylic acid-based polymer. The laminated film according to the item. The gas barrier film layer is
Base film layer and
Claim 1 is a barrier layer located between the base film layer and the first solvent-free adhesive layer, which comprises the barrier layer containing a hydrolysis product of a metal oxide and a phosphorus compound. The laminated film according to any one of 4 to 4. A packaging bag in which the thermoplastic resin layers of the laminated film are laminated so as to face each other and sealed by heat welding of the thermoplastic resin layers.
A packaging bag in which the laminated film is the laminated film according to any one of claims 1 to 8. A method for producing a laminated film in which a gas barrier film layer, a water-based ink layer, a first solvent-free adhesive layer, an intermediate base material layer, a second solvent-free adhesive layer, and a thermoplastic resin layer are arranged in this order.
Forming a water-based ink layer on the gas barrier film layer by printing with ink,
The gas barrier film layer provided with the water-based ink layer and the intermediate base material layer are bonded to each other by coating with a two-component curable urethane-based solvent-free adhesive, and
Including that the intermediate base material layer and the thermoplastic resin layer are bonded by coating with a two-component curable urethane-based solvent-free adhesive.
The ink is a water-based ink containing a polyurethane resin and a water-based cross-linking agent.
The two-component curable urethane-based solventless adhesive contains a partially acid-modified polyol component and a polyisocyanate component.
A method for producing a laminated film, wherein the polyisocyanate component is a mixture of an aliphatic polyisocyanate and an aromatic polyisocyanate. The aqueous cross-linking agent is a carbodiimide compound and
The polyol component is a polyester polyol,
The aliphatic polyisocyanate is hexamethylene diisocyanate.
The method for producing a laminated film according to claim 10, wherein the aromatic polyisocyanate is a xylylene diisocyanate. The coating temperature of the two-component curing type urethane solvent-free adhesive is a temperature at which the cone / plate viscosity becomes 3500 mPa · s or more and 6000 mPa · s or less when 45 minutes have passed from the mixing, claim 10 or 11. The method for producing a laminated film according to. Manufacture of laminated films and
A method for producing a packaging bag, which comprises stacking the thermoplastic resin layers included in the laminated film so as to face each other and sealing the packaging bag by heat welding between the thermoplastic resin layers.
The method for producing a packaging bag, wherein the production of the laminated film is the method for producing a laminated film according to any one of claims 10 to 12.

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