TW201806742A - Laminated structure and method of preparing same - Google Patents

Abstract

Provided is a laminate having a transparent base material, a specific ink layer, a specific adhesive layer and a gas barrier base material in this order, where the ink layer is a dried product or a cured product of an ink composition containing specific polyurethane polyurea resin and a specific amount of vinyl chloride-vinyl acetate copolymer, the adhesive layer is a cured product of an adhesive composition containing a polyisocyanate component (A) and a polyol component (B), and the polyisocyanate component (A) contains an urethane prepolymer (a) having an isocyanate group and 4,4'-diphenylmethane diisocyanate and further contains at least one kind of isocyanate selected from a group consisting of 2,4'-diphenylmethane diisocyanate and tolylene diisocyanate.

Description

Laminated body and manufacturing method thereof

This invention relates to the laminated body which has an ink layer and an adhesive layer, and its manufacturing method, More specifically, it is related to the laminated body which is useful as a packaging material for foods, medical products, cosmetics, etc.

Previously, various plastic films were bonded to each other, or a plastic film and a metal vapor-deposited film or metal foil were bonded by a dry lamination method using a hydroxy / isocyanate-based solvent-based adhesive composition. However, since the dry lamination method uses an adhesive composition containing an organic solvent, special equipment for suppressing and preventing environmental pollution or fire is required.

In recent years, due to the requirements for simple equipment, the demand for deorganizing solvation of the adhesive composition has become stronger, and research on no-solventization is being actively conducted. For example, Patent Document 1 discloses a solventless laminating adhesive composition containing a polyol component (1) and a polyisocyanate component (2) containing two kinds of polyisocyanate compounds. In addition, symbols such as (1) in the literature are expressions described in each literature, and do not agree with the symbols of the invention of the present application (the same applies hereinafter). Furthermore, Patent Document 2 discloses a solventless laminating adhesive composition containing a polyol component (1) and a polyisocyanate component (2) which requires a trifunctional polyisocyanate compound, and the branch point concentration is in a specific range. Molar number of hydroxy group: Molar number of isocyanate group = 1: 1 to 1: 3. Patent Document 3 discloses a solventless adhesive composition containing a polyol component (A) and an isocyanate component (B) that requires isophorone diisocyanate. Patent Document 4 discloses a solventless adhesive composition containing a polyol component (A), a polyisocyanate compound (B), and a powder (C) having a specific particle size. Furthermore, Patent Document 5 discloses an adhesive composition comprising a polyisocyanate component (A) and a polyol component (B), and the polyisocyanate component (A) is a 2,4′-diphenylmethane diisocyanate (A1) A reactive product obtained by reacting with 4,4'-diphenylmethane diisocyanate (a2) and a polyol requiring a polyether polyol (a3) under an excess of isocyanate groups, and the polyol component ( B) A polyester diol (b1) having a number average molecular weight of 500 or more and 3,000 or less is required, and at least one of a diol (b2) or a triol (b3) having a number average molecular weight of 50 or less and less than 500 is required. Further, the second invention of Patent Document 6 describes a plastic film laminate having an outer polyethylene terephthalate film layer (F1), a dry coating layer (P) for printing ink, and coating in this order. Dry film layer (C) of resin, solventless adhesive layer (A), metal vapor deposition layer or metal foil (M), and plastic film layer (F2) inside. Furthermore, Patent Document 7 discloses a two-liquid curing type solventless adhesive composition containing a specific amount of a crystalline polyol component in the total amount of the polyol component (A) and the polyisocyanate component (B). . Patent Document 8 describes an adhesive composition containing a specific polymer containing a urethane prepolymer using a polyether polyol as a raw material and crude diphenylmethane diisocyanate (MDI). An isocyanate component (A) and a specific polyol component (B) containing a polyester diol as an essential component. [Prior Art Literature] [Patent Literature]

[Patent Literature 1] Japanese Patent Laid-Open No. 8-60131 [Patent Literature 2] Japanese Patent Laid-Open Publication No. 2003-96428 [Patent Literature 3] Japanese Patent Laid-Open Publication No. 2006-57089 [Patent Literature 4] Japanese Patent Special Japanese Patent Application Publication No. 2011-162579 [Patent Document 5] Japanese Patent Application Publication No. 2014-159548 [Patent Document 6] Japanese Patent Application Publication No. 2010-280122 [Patent Document 7] Japanese Patent Application Publication No. 2002-249745 [Patent Document 8] Japanese Patent No. 5812219

[Problems to be Solved by the Invention] A laminated body as a packaging material has a laminated structure in which a printing ink layer is formed on a main surface (hereinafter, also referred to as a back surface or a back surface) of a non-surface side of a transparent substrate, and An adhesive layer and a substrate are laminated on the ink layer in this order. The printing ink layer is visually recognized through a main surface (hereinafter, also referred to as a surface and a front surface) of a transparent substrate. The printing ink layer has a form formed on a part of the transparent base material in addition to a form provided on the entire surface of the transparent base material. The printing ink layer includes a single layer or a laminate of a plurality of ink layers. A portion where the printing ink layer is provided may be classified as an ink portion, and a portion not provided may be a plain portion.

Since the solvent-free adhesive composition has no drying step and no solvent discharge, it has the advantages of energy saving and good running cost. In addition, there are many advantages such as no risk of solvent residues in the laminated body after the plastic films are bonded to each other, or the laminated body after the plastic film and the metal foil or metal vapor deposition layer are bonded. However, if a solvent-free adhesive composition and a substrate having a high gas barrier property (hereinafter, also referred to as a gas barrier substrate) provided with a metal vapor-deposited layer on a film are used to form a laminated body as a packaging material, There is a problem that an orange peel-like appearance defect easily occurs in the ink portion.

Patent Documents 1 to 4 describe the principle of using a component having a relatively stable reaction, and specifically using an alicyclic polyisocyanate component or an aliphatic polyisocyanate component as the polyisocyanate component. However, in a polyisocyanate component having a relatively stable reaction, the aging step requires 2 to 5 days at 40 ° C to 50 ° C, and there is a problem that productivity is low. Further, Patent Documents 1 to 4 do not describe improvement of the appearance defect of the ink portion. The aging step refers to a "step of curing the adhesive layer".

Furthermore, Patent Document 5 discloses an adhesive composition that controls reactivity with moisture and has good adhesion performance and a good pot life even under high humidity. However, Patent Document 5 does not mention improvement in the appearance of the ink portion.

Patent Document 6 discloses a case where a dry coating layer (P) of a printing ink is provided between an exterior polyethylene terephthalate film layer (F1) and a dry coating layer (C) of a coating resin. The coating resin constituting the dry film layer (C) of the coating resin is intended to use an adhesive for printing inks to improve the appearance of the ink portion (see paragraphs [0013] and [0014]). However, the processing speed specifically shown in the Example, that is, the application speed of the adhesive is only 10 m / min and is a low speed. Since the solvent-free type adhesive composition is solvent-free, if the coating speed is increased so far, the coating surface is rough, so it is difficult to achieve both the increase in the coating speed and the appearance. In terms of improving productivity, the solvent-free adhesive composition is also expected to have the same level as the solvent-based adhesive composition, for example, a coating speed of about 200 m / min and a good appearance of the ink portion. Laminated body.

On the other hand, Patent Document 7 discloses that by using a solvent-free adhesive composition containing a specific amount of crystalline polyester, even if the application speed is 200 m / min, the purpose of improving the appearance of the ink portion is also desired. . However, since a crystalline polyester is used, it is not possible to improve the appearance defect at low temperature aging at 40 ° C, for example.

In addition, Patent Document 8 describes the principle of applying a coating at a speed of 200 m / min or more and aging at a low temperature for a short period of time to obtain a laminated body having an excellent appearance. However, an improvement in the appearance of the printed portion is desired.

The object of the present invention is to use a substrate having excellent gas barrier properties (a substrate having an oxygen permeability at 25 ° C of 100 cc / (m ² · day · atm) or less) at a high speed (for example, a coating speed). 200 m / min) The adhesive composition was applied, and a laminate having a good appearance of the printed portion was provided by low temperature (for example, 40 ° C.) and short-term aging. [Means for solving problems]

The present invention was found to solve the problems of the present invention in the following aspects, and completed the present invention. That is, one embodiment of the present invention relates to a laminated body including, in order, a first substrate having visible light permeability, a specific ink layer, a specific adhesive layer, and an oxygen transmission coefficient at 25 ° C of 100 cc / ( m ² · day · atm). That is, the ink layer satisfies all the conditions (1) to (5) below, and the adhesive layer satisfies all the conditions (11) to (15) below. (1) The ink layer is a dried or cured product of an ink composition containing a polyurethane polyurea resin, a vinyl chloride-vinyl acetate copolymer, a pigment, and an organic solvent. (2) The vinyl chloride-vinyl acetate copolymer is contained in a total of 100 mass% of the polyurethane polyurea resin and the vinyl chloride-vinyl acetate copolymer in an amount of 5 to 40 mass%. Thing. (3) The polyurethane polyurea resin contains a polyurethane unit having a structural unit derived from a polymer polyol having a number average molecular weight of 400 to 5000 and a structural unit derived from a polyisocyanate compound. Segment, and a chain extension unit derived from a compound having an amine group, the polyurethane block and the chain extension unit are bonded by a urea bond, and the number average molecular weight is as high as 400-5000 100% by mass of the molecular polyol includes 5% by mass or more of the polyester polyol. (4) The mass average molecular weight of the polyurethane polyurea resin is 15,000 to 70,000. (5) The total concentration of the urethane bond and the urea bond contained in 1 g of the polyurethane polyurea resin is 1.3 mmol / g to 2.4 mmol / g. (11) The said adhesive layer is a hardened | cured material of the adhesive composition containing a polyisocyanate component (A) and a polyol component (B). (12) The polyisocyanate component (A) includes an urethane prepolymer (a) having an isocyanate group and 4,4'-diphenylmethane diisocyanate, and further includes a member selected from 2,4'-di At least one isocyanate in the group consisting of phenylmethane diisocyanate and toluene diisocyanate. (13) The urethane prepolymer having the isocyanate group (a) is a reaction product of an isocyanate component and a polyol requiring a polyether polyol, wherein the isocyanate component requires 4,4'-diphenyl Methane diisocyanate and further including at least one selected from the group consisting of 2,4'-diphenylmethane diisocyanate and toluene diisocyanate, or a combination of 4,4'-diphenylmethane diisocyanate and a polyol A reaction product, and a mixture of an isocyanate component and a reaction product of a polyol, and at least one of the polyols requires a polyether polyol, wherein the isocyanate component is selected from the group consisting of 2,4'-diphenylmethane diisocyanate, toluene di At least one of the group consisting of isocyanates. (14) The polyol component (B) needs to contain a polyester polyol having a number average molecular weight of 500 or more and 3,000 or less. (15) The total amount of 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate and toluene diisocyanate contained in 100% by mass of the adhesive composition is 10% by mass ～ 34% by mass.

Here, "having visible light permeability" means that the ink layer bonded to the first substrate can be visually recognized through the first substrate, and includes color and transparency in addition to colorless and transparent. The laminated body may be laminated with other layers within a range not departing from the gist of the present invention. The oxygen transmission rate in this specification is obtained by measuring at 25 ° C. Oxygen permeability 1 cc / (m ² · day · atm) is 9.87 mL / (m ² · day · MPa), so 100 cc / (m ² · day · atm) is 987 mL / (m ² · day · MPa) ). The "dried product or cured product of the ink composition" refers to an ink layer that is cured by forming an ink layer or a layer of the ink composition obtained by drying a layer formed using the ink composition. The "chain extension unit" refers to a terminal blocking agent and / or a chain elongating agent.

Another embodiment of the present invention relates to a laminated body, wherein the pigment contained in the ink layer is titanium oxide.

Furthermore, another embodiment of the present invention relates to a laminated body, wherein the second substrate is formed by laminating a transparent film and a metal vapor-deposited layer on a main surface of the transparent film, and the metal vapor The plating layer is in contact with the adhesive layer. Here, the “transparent film” refers to a film having visible light transmittance, and is defined in the same manner as the first base material layer.

Furthermore, another embodiment of the present invention relates to a method for manufacturing a laminated body, wherein the laminated body is sequentially laminated: a first substrate having visible light permeability, a specific ink layer, a specific adhesive layer, and a 25 ° C The second substrate having an oxygen transmission rate of 100 cc / (m ² · day · atm) or less includes the following steps (I) to (VI). (I-1) A step of preparing a polyurethane polyurea resin having a number average molecular weight of 15,000 to 70,000, which is a polymer polyol having a number average molecular weight of 400 to 5,000. A reaction product with a polyisocyanate compound and a compound having an amine group. The high-molecular-weight polyol having a number average molecular weight of 400 to 5000 includes 100% by mass or more of a polyester polyol and 100% by mass of a polyurethane. The total concentration of the urethane bond and the urea bond contained in 1 g of the polyurea resin is 1.3 mmol / g to 2.4 mmol / g. (I-2) a step of preparing an ink composition containing the polyurethane polyurea resin, a vinyl chloride-vinyl acetate copolymer, a pigment, and an organic solvent, and the polyurethane The total amount of 100% by mass of the ester polyurea resin and the vinyl chloride-vinyl acetate copolymer contains 5 to 40% by mass of the vinyl chloride-vinyl acetate copolymer. (II-1) A step of preparing a polyisocyanate component (A) containing a urethane prepolymer (a) having an isocyanate group and 4,4'-diphenylmethane di An isocyanate, further comprising at least one isocyanate component selected from the group consisting of 2,4'-diphenylmethane diisocyanate and toluene diisocyanate, and the urethane prepolymer (a) is obtained by Reacting an isocyanate component with a polyol that requires a polyether polyol under conditions where the isocyanate group is excessive, wherein the isocyanate component requires 4,4'-diphenylmethane diisocyanate and further comprises a member selected from 2,4'-diphenyl At least one of the group consisting of methylmethane diisocyanate and toluene diisocyanate, or obtained by separately reacting an isocyanate component with a polyol that requires a polyether polyol under the condition of excess isocyanate groups, and then mixing, Wherein the isocyanate component requires 4,4'-diphenylmethane diisocyanate and is at least selected from the group consisting of 2,4'-diphenylmethane diisocyanate and toluene diisocyanate One. (II-2) A step of preparing an adhesive composition comprising the polyisocyanate component (A) and a polyol component (B which needs to contain a polyester polyol having a number average molecular weight of 500 to 3000) ) Mixed, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane contained in the total 100% by mass of the polyisocyanate component (A) and the polyol component (B) The total amount of diisocyanate and toluene diisocyanate is 10% to 34% by mass. (III) a step of applying the ink composition on the first substrate and drying or curing the ink composition to obtain the ink layer. (IV) A step of applying the adhesive composition on the ink layer to form a precursor of the adhesive layer. (V) a step of superimposing the second substrate on a precursor of the adhesive layer. (VI) After step (V), a step of hardening the precursor of the adhesive layer to form the adhesive layer.

Furthermore, another embodiment of the present invention relates to another manufacturing method of a laminated body, wherein the laminated body is sequentially laminated: a first substrate having visible light permeability, a specific ink layer, a specific adhesive layer, and 25 ° C. The second substrate has an oxygen permeability of 100 cc / (m ² · day · atm) or lower. That is, it is related with the manufacturing method of the laminated body which consists of the following steps (I)-(III) and (VII)-(IX). (I-1) A step of preparing a polyurethane polyurea resin having a number average molecular weight of 15,000 to 70,000, which is a polymer polyol having a number average molecular weight of 400 to 5,000. A reaction product with a polyisocyanate compound and a compound having an amine group. The high-molecular-weight polyol having a number average molecular weight of 400 to 5000 includes 100% by mass or more of a polyester polyol and 100% by mass of a polyurethane. The total concentration of the urethane bond and the urea bond contained in 1 g of the polyurea resin is 1.3 mmol / g to 2.4 mmol / g. (I-2) a step of preparing an ink composition containing the polyurethane polyurea resin, a vinyl chloride-vinyl acetate copolymer, a pigment, and an organic solvent, and the polyurethane The total amount of 100% by mass of the ester polyurea resin and the vinyl chloride-vinyl acetate copolymer contains 5 to 40% by mass of the vinyl chloride-vinyl acetate copolymer. (II-1) A step of preparing a polyisocyanate component (A) containing a urethane prepolymer (a) having an isocyanate group and 4,4'-diphenylmethane di An isocyanate, further comprising at least one isocyanate component selected from the group consisting of 2,4'-diphenylmethane diisocyanate and toluene diisocyanate, and the urethane prepolymer (a) is obtained by Reacting an isocyanate component with a polyol that requires a polyether polyol under conditions where the isocyanate group is excessive, wherein the isocyanate component requires 4,4'-diphenylmethane diisocyanate and further comprises a member selected from 2,4'-diphenyl At least one of the group consisting of methylmethane diisocyanate and toluene diisocyanate, or obtained by separately reacting an isocyanate component with a polyol that requires a polyether polyol under the condition of excess isocyanate groups, and then mixing, Wherein the isocyanate component requires 4,4'-diphenylmethane diisocyanate and is at least selected from the group consisting of 2,4'-diphenylmethane diisocyanate and toluene diisocyanate One. (II-2) A step of preparing an adhesive composition comprising the polyisocyanate component (A) and a polyol component (B which needs to contain a polyester polyol having a number average molecular weight of 500 to 3000) ) Mixed, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane contained in the total 100% by mass of the polyisocyanate component (A) and the polyol component (B) The total amount of diisocyanate and toluene diisocyanate is 10% to 34% by mass. (III) a step of applying the ink composition on the first substrate and drying or curing the ink composition to obtain the ink layer. (VII) A step of applying the adhesive composition on the second substrate to form a precursor of the adhesive layer. (VIII) a step of overlapping the ink layer on a precursor of the adhesive layer. (IX) After step (VIII), the precursor of the adhesive layer is hardened to form the adhesive layer. [Effect of the invention]

According to the present invention, when a substrate having excellent gas barrier properties (a substrate having an oxygen permeability at 25 ° C of 100 cc / (m ² · day · atm) or less) is used, it has the following excellent effects: high speed (For example, the application speed is 200 m / min.) The adhesive composition is applied, and a laminated body having a good appearance of the printed portion can be provided by, for example, low temperature (40 ° C) and short-term aging.

An example of an embodiment to which the present invention is applied will be described below. In addition, as long as it is consistent with the gist of the present invention, other embodiments are naturally included in the scope of the present invention. In addition, the specific numerical value in this specification is a value calculated | required by the method disclosed in embodiment or an Example. The specific numerical values “A to B” in the present specification include a numerical value A and a numerical value B, and mean a range larger than the numerical value B and smaller than the numerical value B. As long as the various components appearing in this specification are not specifically noted, they may be independent of each other, or two or more of them may be used in combination.

The laminated body according to this embodiment is a first substrate having visible light permeability, an ink layer, an adhesive layer, and a second substrate having an oxygen transmittance of 100 cc / (m ² · day · atm) or less at 25 ° C. in this order. Made of wood.

<Ink Layer> The ink layer is a dried or cured product of the ink composition. As described above, the ink composition contains a polyurethane polyurea resin, a vinyl chloride-vinyl acetate copolymer, a pigment, and an organic solvent. First, the polyurethane polyurea resin contained in the ink composition will be described. The polyurethane polyurea resin in this embodiment is a reaction product of a urethane prepolymer having an isocyanate group and a compound having an amine group, and the urethane prepolymer having an isocyanate group is The substance is formed by reacting a polymer polyol with a polyisocyanate compound. In other words, the polyurethane polyurea resin has a polyurethane block (equivalent to a residue of a urethane prepolymer), a structural unit derived from a polymer polyol, and A structural unit of a polyisocyanate compound; and a chain extension unit (corresponding to a residue of a compound having an amine group) derived from a compound having an amine group. Further, the polyurethane block and the chain extension unit are bonded by a urea bond.

The polymer polyol is known as a polymer ink for gravure inks and flexographic inks, and can be obtained by a polymerization reaction, a condensation reaction, a natural product, or the like. Most polymer polyols have a number average molecular weight of 400 to 10,000. The polyurethane polyurea resin of this embodiment needs to contain structural units derived from polymer polyols having a number average molecular weight of 400 to 5000. Polyurethane polyurea resin has a moderate flexibility by including structural units derived from a polymer polyol having a number average molecular weight of 400 or more, and therefore, it is leveled when the ink composition is printed on the first substrate. It is excellent in properties, and the appearance of the obtained laminated body is improved. In addition, by including a structural unit derived from a polymer polyol having a number average molecular weight of 5,000 or less, the cohesion of the ink layer obtained is improved, and the penetration of the ink layer by the isocyanate monomer in the adhesive composition is suppressed, and the appearance of the laminate is suppressed. And the lamination strength is improved.

As the structure of the polymer polyol of the present embodiment, various known polymer polyols generally used in the production of polyurethane resins can be used, and they can be used alone or in combination of two or more. Examples include polyether polyols (1) of polymers or copolymers such as formaldehyde, ethylene oxide, propylene oxide, and tetrahydrofuran; ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2 Methyl-1,3 propylene glycol, 2ethyl-2butyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl 1,5-pentanediol, hexanediol, octanediol, 1,4-butynediol, 1,4-butenediol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerol, Trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, sorbitol, pentaerythritol and other saturated or unsaturated low molecular polyols, and Adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, suberic acid, nonyl Polyester polyols (2) obtained by dehydration condensation or polymerization of polycarboxylic acids such as diacid, sebacic acid, pyromellitic acid, pyromellitic acid and the like, or these anhydrides; Compounds, such as polycaprolactone, polyvalerolactone, poly (β-methyl-γ-valerolactone), etc. Polyester polyols (3) obtained; polycarbonates obtained by the reaction of the low-molecular-weight polyols and the like with, for example, dimethyl carbonate, diphenyl carbonate, ethylene carbonate, phosgene and the like Polyols (4); polybutadiene diols (5); diols (6) obtained by adding ethylene oxide or propylene oxide to bisphenol A; by more than one in one molecule Acrylic polyols obtained by copolymerizing hydroxyethyl, hydroxypropyl acrylate, acrylate hydroxybutyl, etc., or corresponding methacrylic acid derivatives of these compounds with, for example, acrylic acid, methacrylic acid or their esters (7 )Wait.

Among polymer polyols, polyester polyols are particularly excellent in terms of the adhesion of the ink layer to the first substrate and the solubility of the ink composition to the solvent. In the polyurethane polyurea resin in this embodiment, 100% by mass of the polymer polyol having a number average molecular weight of 400 to 5,000 includes polyester polyols in an amount of 5% by mass or more. By containing 5% by mass or more of the polyester polyol, it is possible to suppress the penetration of the adhesive agent component into the obtained ink layer, and to improve the appearance and lamination strength of the laminate. The content of the polyester polyol is preferably from 20% to 90% by mass, and more preferably from 40% to 80% by mass, among 100% by mass of the polymer polyol. As the polyester polyols, one or more selected from the group consisting of 2methyl-1,3-propanediol, 2ethyl-2butyl-1,3propanediol, and 3-methyl-1,5pentanediol are used. Since a polyester polyol obtained by polymerizing a diol having a branched structure and adipic acid has a branched structure, it is particularly excellent in adhesion and solubility to a substrate. Particularly preferred is a polyester polyol obtained by polymerizing 3-methyl-1,5-pentanediol and adipic acid.

Among the polymer polyols, in addition to the polyester polyols that need to be included, polymer polyols other than one or more polyester polyols may be used in combination. As the polymer polyols used in combination, it is preferred that Polyether polyols having high adhesion to the first substrate and excellent solubility in solvents. As a polyether polyol, it is preferable that it is a polymer of propylene oxide which has moderate flexibility from the point of the adhesiveness with respect to a base material.

In addition to the polymer polyol, a low-molecular polyol having a number average molecular weight of 400 or less may be optionally contained. As the structure of the low-molecular-weight polyol, various known low-molecular-weight polyols generally used in the production of polyurethane resins can be used, and they may be used alone or in combination of two or more. Examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3propanediol, 2ethyl-2butyl-1,3propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1,5-pentanediol, hexanediol, octanediol, 1,4-butynediol, 1,4- Butenediol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanediol Saturated or unsaturated low-molecular-weight polyols such as triol, sorbitol, pentaerythritol, low-molecular-weight diols containing carboxylic acids such as dimethylolbutanoic acid and dimethylolpropionic acid, and trimethylolpropane Molecular triol and so on. By using these low-molecular-weight diols, adjustment of urethane bond density and introduction of a functional group into a polyurethane polyurea resin become easy.

Examples of the polyisocyanate compound used in the formation of the polyurethane polyurea resin include various well-known aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates commonly used in the production of polyurethane resins. Isocyanate, etc. Examples include 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, di Alkyl diphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, toluene diisocyanate, butane-1,4- Diisocyanate, hexamethylene diisocyanate, isopropyl diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, cyclohexane-1 , 4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dimethyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis (isocyanate methyl) ring Hexane, methylcyclohexane diisocyanate, norbornane diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, toluene diisocyanate, bis-chloromethyl-di Phenylmethane-diisocyanate, 2,6-diisocyanate-benzyl chloride or conversion of the carboxyl group of a dimer acid to isopropyl Dimeric diisocyanates and the like made of cyanate groups. These diisocyanate compounds can be used alone or in combination of two or more.

Among the polyisocyanate compounds, isophorone diisocyanate, toluene diisocyanate, and 4,4'-diphenylmethane diisocyanate are preferred. From the viewpoint of solubility, isophorone diisocyanate is more preferable. .

A compound having an amine group used in forming a polyurethane polyurea resin is useful as a chain elongator for increasing the molecular weight of the urethane prepolymer, and for making a polyurethane polyurea. Resin's end stopper for which the reaction stops.

Examples of the chain extender include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, and dicyclohexylmethane-4,4 ' -Diamines, etc. Furthermore, as a chain extender which can add a hydroxyl group to the side chain of a polyurethane polyurea resin, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, and 2-hydroxy group can also be used. Ethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2- Amines having a hydroxyl group in the molecule such as hydroxypropylethylenediamine and di-2-hydroxypropylethylenediamine. The chain elongating agent may be used singly or in combination of two or more kinds. From the viewpoint that the obtained ink composition exhibits excellent solubility in a solvent and improves workability during printing, it is preferable to use isophoronediamine and 2-hydroxyethylethylenediamine in combination.

As the terminal blocking agent, for example, in addition to dialkyl monoamines such as di-n-butylamine, monoethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol, and tris (hydroxymethyl) Monoamines having a hydroxyl group, such as aminoaminomethane and 2-amino-2-ethyl-1,3-propanediol. Further examples include glycine, alanine, glutamic acid, taurine, aspartic acid, aminobutyric acid, valine, aminocaproic acid, aminobenzoic acid, and aminom-phenylene. Monoamine amino acids such as dicarboxylic acid and aminosulfonic acid. By using a monoamine having a hydroxyl group such as monoethanolamine, a hydroxyl group can be added to the terminal of the polyurethane polyurea resin.

In addition, as the terminal blocking agent, in addition to the compound having an amine group, a monovalent active hydrogen compound may be used. Examples of the compound include alcohols such as ethanol and isopropanol.

The polyurethane polyurea resin in this embodiment is obtained by reacting a urethane prepolymer having an isocyanate group at a terminal and a compound having an amine group. That is, first, an inactive solvent is used in the isocyanate group as needed, and further, a polyol is used to react a polyhydric alcohol containing a polymer polyol with a polyisocyanate compound at a temperature of 10 ° C to 100 ° C, if necessary. Isocyanate-based urethane prepolymer. Then, the urethane prepolymer and the compound having an amine group are reacted at 10 ° C to 80 ° C.

The method for reacting the urethane prepolymer with a compound having an amine group is a method in which a solution of a compound having an amine group is slowly added dropwise to a solution of the urethane prepolymer, or a method having a reaction with an amine group In this embodiment, a method such as a method in which a urethane prepolymer solution is added dropwise to a solution of a compound can be performed by any method.

The mass average molecular weight of the polyurethane polyurea resin in this embodiment is 15,000 to 70,000, and preferably 30,000 to 60,000. When the mass average molecular weight is 15,000 or more, since the pigment dispersibility is excellent, the obtained ink composition is excellent in color development and the cohesive force of the ink layer is also improved. Moreover, since it exhibits high cohesion, it is possible to suppress the penetration of the adhesive composition into the ink layer. Therefore, the appearance and laminated strength of the laminated body are improved. When the mass average molecular weight is 70,000 or less, the ink composition obtained when printed on the first substrate is excellent in leveling property, and a smooth ink layer surface without unevenness due to poor leveling can be obtained. Therefore, voids and / or bubbles are less likely to occur at the interface between the ink layer and the adhesive layer, and the appearance of the laminate is improved. Furthermore, work efficiency in a printing step using the obtained ink composition is also improved.

The urethane bond and the urea bond in this embodiment refer to a bond obtained by a reaction between a hydroxyl group and an isocyanate group and a bond obtained by a reaction between an amine group and an isocyanate group, and the so-called urethane bond shown here The total concentration of urea bonds refers to the total number of moles of each bond contained in 1 g of the polyurethane polyurea resin.

The total concentration of the urethane bond and the urea bond of the polyurethane polyurea resin in this embodiment is 1.3 mmol / g to 2.4 mmol / g, preferably 1.4 mmol / g to 2 mmol / g . When the total concentration of the urethane bond and the urea bond is 1.3 mmol / g or more, the adhesive layered in the obtained ink layer becomes difficult to penetrate, and the appearance of the laminated body becomes good. When it is 2.4 mmol / g or less, the solubility with respect to a solvent improves and the leveling property of the obtained ink composition becomes favorable. As a result, a more uniform ink layer can be formed, and the external appearance of a laminated body becomes favorable.

The concentration of the urethane bond can be determined by the number-average molecular weight of all polyols used in the reaction to obtain the urethane prepolymer, or the hydroxyl group and the isocyanate in the reaction to obtain the urethane prepolymer. Either the molar ratio of the base, that is, the NCO / OH ratio is controlled. The concentration of the urea bond can be determined by the number average molecular weight of all the compounds having an amine group, or the isocyanate group of the urethane prepolymer and the primary or secondary amine group in the compound having an amine group. The Mohr ratio, that is, the NCO / OH ratio is controlled. The total concentration of the urethane bond and the urea bond of the polyurethane polyurea resin in this embodiment is 1.3 mmol / g to 2.4 mmol / g, and each of the urethane bond and the urea bond is The concentration is preferably within a range of 0.5 mmol / g to 1.2 mmol / g.

Next, a vinyl chloride-vinyl acetate copolymer (hereinafter, sometimes referred to as vinyl chloride vinyl acetate) contained in the ink composition in this embodiment will be described. The ink composition in this embodiment contains a vinyl chloride-vinyl acetate copolymer. The vinyl chloride-vinyl acetate copolymer requires a vinyl chloride site and a vinyl acetate site, and may have a vinyl alcohol modified site or a maleic acid modified site. Among 100% by weight of vinyl chloride-vinyl acetate copolymer, 85% to 95% by weight of vinyl chloride portions are preferably contained, and 1% to 15% by weight of vinyl acetate portions are included. Vinyl chloride-vinyl acetate The molecular weight of the ester copolymer is preferably in the range of 20,000 to 80,000. The vinyl chloride-vinyl acetate copolymer is commercially available, and examples thereof include Solbin C, CL, CH, CN, CNL, C5R, A, AL, TA5R, TA3, TAO, manufactured by Nissin Chemical Industry Co., Ltd. M5, VINNOL E15 / 45, H14 / 36, H15 / 42, H40 / 43, H40 / 50, H20 / 45, H15 / 45M, H30 / 48M, H15 / 45M manufactured by WACKER Wait.

The vinyl chloride-vinyl acetate copolymer is excellent in compatibility with other components in the polyurethane polyurea resin and the ink composition, and therefore, it is suitable for producing printed articles with good appearance without pinholes and the like. Furthermore, the chemical resistance of the vinyl chloride site can suppress the penetration of the adhesive composition component into the ink layer. In addition, by the plasticity of the vinyl acetate site, the adhesion of the ink layer to the first substrate is improved, and a laminate having good lamination strength can be obtained. It is important that the ink composition in this embodiment contains 5% to 40% by mass of vinyl chloride in 100% by mass of the total solid content of the polyurethane polyurea resin and the vinyl chloride-vinyl acetate copolymer. The vinyl acetate copolymer preferably contains 10 to 30% by mass. When it is 5 mass% or more, the adhesive does not easily penetrate into the ink layer, and the appearance of the laminated body becomes good. On the other hand, when it is 40% by mass or less, the laminated body has good lamination strength.

In the vinyl chloride-vinyl acetate copolymer, a vinyl chloride-vinyl acetate copolymer containing a hydroxyl group is used in a solvent other than toluene (hereinafter, also referred to as non-toluene), or methyl ethyl ketone and methyl isobutyl. Solvents other than ketone solvents such as ketones (hereinafter also referred to as non-ketones) are particularly excellent in solubility. When the ink composition is produced using a non-toluene or / and non-ketone solvent, and further printing is performed, the vinyl chloride-vinyl acetate copolymer containing the hydroxyl group is more preferable. Examples of the vinyl chloride-vinyl acetate copolymer containing a hydroxyl group include Solbin A, AL, TA5R, TAO, and the like.

Various resins other than the said polyurethane polyurea resin and a vinyl chloride-vinyl acetate copolymer can be used for the ink composition in this embodiment according to a use or a base material. Examples of the resin to be used include polyurethane polyurea resins other than those described above, polyurethane resins, vinyl chloride-acrylate copolymers, chlorinated polypropylene resins, and ethylene- Vinyl acetate copolymer resin, vinyl acetate resin, polyamide resin, nitrocellulose resin, acrylic resin, polyester resin, alkyd resin, polyvinyl chloride resin, rosin resin, rosin modified maleic acid resin, Terpene resin, phenol-modified terpene resin, ketone resin, cyclized rubber, chlorinated rubber, butyral, petroleum resin, and these modified resins. Especially preferred is vinyl chloride-vinyl acetate copolymerization. These resins can be used singly or in combination of two or more. The content of the resin is preferably 0.5% to 20% by mass relative to 100% by mass of the solid content of the ink composition.

In the ink composition in this embodiment, an inorganic pigment and an organic pigment can be used as the pigment. The pigment is preferably an amount sufficient to ensure the density of the printed matter, that is, it is contained in a proportion of 1 to 50% by mass in 100% by mass of the ink composition. These pigments can be used alone or in combination of two or more.

Examples of the organic pigment include users of ordinary inks, paints, and recording materials. Examples include azo-based, phthalocyanine-based, anthraquinone-based, fluorene-based, violone-based, quinacridone-based, thioindigo-based, dioxazine-based, isoindolinone-based, and quinophthalone System, methylimine azo system, diketopyrrolopyrrole system, isoindoline system, and the like. As the blue ink, copper phthalocyanine is preferably used. In terms of cost and light resistance, the transparent yellow ink is preferably C.I. Pigment No Yellow 83.

On the other hand, examples of the inorganic pigment include titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, aluminum hydroxide, chromium oxide, silicon dioxide, carbon black, aluminum, mica, and the like. .

The ink layer includes a single layer or multiple layers, and can be made into any laminated structure according to the application. Usually, a multi-color ink layer is formed, and then a white ink layer is laminated. In this case, the white ink layer is in direct contact with the adhesive layer laminated on it. Therefore, the effect of suppressing the permeation of the components of the adhesive layer with respect to the white ink layer on the appearance of the laminated body is maximized. Therefore, it is preferable to use a white inorganic pigment as the pigment of the ink layer, and among these, it is preferable to use titanium oxide. Titanium oxide is excellent in chemical resistance, and therefore can suppress the penetration of the adhesive into the white ink layer, and is also suitable for obtaining a laminated body having a good appearance in terms of coloring power and hiding power. Titanium oxide is preferably subjected to a surface treatment using an inorganic oxide, and examples thereof include silicon dioxide treatment, aluminum oxide treatment, and silicon dioxide / alumina treatment.

The ink composition in this embodiment can also be used as a single-liquid type ink composition. For the purpose of the laminated body and further improving the heat resistance and water resistance, a known isocyanate-based hardener can be added and used as a two-liquid type ink组合 物。 Composition. As the isocyanate-based curing agent, for example, each of polyisocyanates (additions) of toluene diisocyanate (Tluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and hexamethylene diisocyanate (HDI)) can be used. Adult), biuret-type polyisocyanate (biuret), isocyanurate-type polyisocyanate (isocyanurate), and the like. Examples include adducts obtained by reacting 1 mole of trimethylolpropane with 3 moles of HDI, biuret bodies obtained by reacting 1 mole of water with 3 moles of HDI, and cyclic tris of HDI Isocyanurate bodies and the like obtained by quantifying the reaction. When used as a two-liquid type printing ink, the addition amount of the polyisocyanate-based hardener is preferably 3% to 30% by mass based on 100% by mass of the solid content in the ink composition.

As the organic solvent used in the ink composition in this embodiment, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate, propylene glycol monoethyl ether acetate, and propylene glycol monomethyl ester can be used. Ester solvents such as ether acetate, alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, propylene glycol monoethyl ether, and propylene glycol monomethyl ether, methyl cyclohexane, ethyl cyclohexane, etc. Known solvents such as hydrocarbon solvents. In recent years, from the viewpoint of working environment, aromatic organic solvents such as toluene and xylene, or ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone have been required to be removed. In the ink composition in this embodiment, Also, the solvent for removing it is preferably used.

The ink composition in this embodiment can be produced by dissolving and / or dispersing a resin, a pigment, and the like in an organic solvent. A known method can be used without limitation. As specific examples, pigments, polyurethane polyurea resins, vinyl chloride-vinyl acetate copolymers, other resins, and other compounds as needed can be produced. A pigment dispersion obtained by dispersing any of them in an organic solvent, and further blending the remaining polyurethane polyurea resin, vinyl chloride-vinyl acetate copolymer, other resins, and organic solvents in the obtained pigment dispersion. And other compounds as needed to produce an ink composition. The step of obtaining a pigment dispersion is also referred to as a pulverization step. Polyurethane polyurea resin, vinyl chloride-vinyl acetate copolymer, and other resins, organic solvents, and if necessary, will be blended in the obtained pigment dispersion. Steps of other compounds and the like are also referred to as thinning steps.

In order to stably disperse the pigment in an organic solvent, a dispersant may be used in combination. As the dispersant, an anionic, nonionic, cationic, or diionic surfactant can be used. From the viewpoint of storage stability of the ink, the dispersant is preferably 0.01% by mass or more with respect to the total mass of the ink, and from the viewpoint of lamination adaptability, it is preferably contained in the ink at 5% by mass or less.组合 物。 Composition. Furthermore, it is more preferable to contain it in the range of 0.05 mass%-2 mass%.

The particle size distribution of the pigment in the pigment dispersion can be adjusted by appropriately adjusting the size of the pulverizing medium of the disperser, the filling rate of the pulverizing medium, the dispersion treatment time, the ejection speed of the pigment dispersion, the viscosity of the pigment dispersion, and the like. As a dispersing machine, a roll mill, a ball mill, a gravel mill, a grinding agent, a sand mill, etc. which are generally used can be used.

In the case where the ink composition contains bubbles or unexpectedly large particles, etc., the quality of the printed matter is reduced, and therefore it is preferably removed by filtration or the like. The filter can be a known one.

From the viewpoint of preventing the pigment from settling and appropriately dispersing, the viscosity of the ink composition produced by the method is preferably 10 mPa · s or more. In terms of workability efficiency when the ink composition is manufactured or printed, From a viewpoint, it is preferable that it is the range below 1000 mPa * s. The viscosity is a viscosity measured at 25 ° C. using a B-type viscosity meter manufactured by Tokimec.

<Adhesive layer> The adhesive layer of this embodiment is a hardened | cured material of the adhesive composition containing a polyisocyanate component (A) and a polyol component (B). First, the polyisocyanate component (A) will be described. Hereinafter, 4,4'-diphenylmethane diisocyanate is sometimes referred to as 4,4'-MDI, and 2,4'-diphenylmethane diisocyanate is sometimes referred to as 2,4'-MDI. Toluene diisocyanate is referred to as TDI.

The polyisocyanate component (A) contains an urethane prepolymer (a) having an isocyanate group and 4,4'-MDI, and further contains at least one selected from the group consisting of 2,4'-MDI and TDI. An isocyanate compound. The urethane prepolymer (a) is obtained by reacting an isocyanate component with a polyol under an excess of isocyanate groups, and is a reaction product of an isocyanate component and a polyol requiring a polyether polyol, wherein The isocyanate component requires 4,4'-MDI and contains at least one selected from the group consisting of 2,4'-MDI and TDI, or each of the isocyanate component and at least one of the polyols is a polyether polyol. A mixture of reaction products of a polyol, wherein the isocyanate component requires 4,4'-MDI and is at least one selected from the group consisting of 2,4'-MDI and TDI.

That is, examples of the urethane prepolymer (a) used in this embodiment include (a1) to (a6). (A1) The reaction product of 4,4'-MDI and 2,4'-MDI with a polyol that requires a polyether polyol. (A2) The reaction product of 4,4'-MDI with TDI and a polyol requiring a polyether polyol. (A3) The reaction product of 4,4'-MDI and 2,4'-MDI and TDI with a polyol that requires a polyether polyol. (A4) A mixture of a reaction product of 4,4'-MDI and a polyol and a reaction product of 2,4'-MDI and a polyol. (A5) A mixture of a reaction product of 4,4'-MDI and a polyol and a reaction product of TDI and a polyol. (A6) A mixture of a reaction product of 4,4'-MDI and a polyol, a reaction product of 2,4'-MDI and a polyol, and a mixture of a reaction product of TDI and a polyol.

In the case of (a4) to (a6) in which a plurality of reaction products are mixed, the polyether polyol may be included in at least one reaction product of the polyols used. That is, for example, in the case of (a4), the following aspects are included. (A4-1) A mixture of a reaction product of 4,4'-MDI and a polyol requiring a polyether polyol and a reaction product of 2,4'-MDI and a polyol other than the polyether polyol. (A4-2) A mixture of a reaction product of 4,4'-MDI with a polyol other than a polyether polyol, and a reaction product of 2,4'-MDI with a polyol requiring a polyether polyol. (A4-3) A mixture of a reaction product of 4,4'-MDI with a polyol requiring a polyether polyol and a reaction product of 2,4'-MDI with a polyol requiring a polyether polyol. In addition, the "polyol requiring a polyether polyol" may be only a polyether polyol, or a polyether polyol and a polyol other than a polyether polyol may be used in combination. Therefore, (a4-1) further includes the following aspects. (A4-1-1) A mixture of a reaction product of 4,4'-MDI and a polyether polyol and a reaction product of 2,4'-MDI and a polyol other than the polyether polyol. (A4-1-2) Reaction products of 4,4'-MDI and polyether polyols, reaction products of 4,4'-MDI and polyols other than polyether polyols, and 2,4'-MDI and A mixture of reaction products of polyols other than polyether polyols. Each of the polyether polyols and polyols other than the polyether polyols may be used alone or in combination of two or more.

In addition, in the cases of (a1) to (a3), 4,4'-MDI and 2,4'-MDI can be mixed with a polyol that requires a polyether polyol, and each isocyanate can be sequentially reacted with Polyol polyols are required for polyol reactions.

Furthermore, the reaction products of (a1) to (a3) may be used in combination with each other, or the mixtures of (a4) to (a6) may be used in combination with each other, or the reaction products of (a1) to (a3) and (a4) to (a6) ) Mixture.

The polyol used to form the urethane prepolymer (a) will be described. The polyol contains a polyether polyol as an essential component, and may further contain a polyester polyol. Polyether polyols generally have a lower viscosity in the molten state than polyester polyols. Therefore, polyamine polyols have a carbamate in a polyisocyanate component (A) that is a constituent component of a solventless adhesive composition. As the polyol for the ester prepolymer, a polyether polyol is important. By further using the polyester polyol in combination, compatibility with a polyol component (B) to be described later can be improved, and cohesion of the adhesive layer can be improved. When the polyester polyol is used in combination, the viscosity of the adhesive composition is preferably 50% by mass or less in 100% by mass of the polyol.

Examples of the polyether polyols include low-molecular-weight polyols such as water, ethylene glycol, propylene glycol, trimethylolpropane, and glycerin as starting agents, and examples thereof include ethylene oxide, propylene oxide, and butylene oxide. A polyether polyol obtained by polymerizing an oxetane compound, such as tetrahydrofuran.

As the polyether polyol, in addition to difunctionality, trifunctional or higher functionality can also be used. Further, a plurality of functional groups having different numbers may be used in combination. The polyether polyol is preferably one having a number average molecular weight of 100 or more and 5000 or less. Further, a plurality of different molecular weights may be used in combination.

Examples of the polyester polyol include a polyester polyol obtained by reacting a polycarboxylic acid component and a diol component. Examples of the polycarboxylic acid component include polycarboxylic acids such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, and sebacic acid, or these dialkyl esters or mixtures thereof. Examples of the diol component include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, and 3 , 3'-Dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol (Polytetramethylene Ether Glycol) and other diols or a mixture of these.

Examples of the low-molecular-weight diol include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, Low-molecular-weight diols such as 3,3'-dimethylolheptane and 2-methyl-1,3-propanediol or a mixture of these.

As described above, the polyisocyanate component (A) in this embodiment includes a urethane prepolymer (a) having an isocyanate group and 4,4'-MDI, and further includes a member selected from 2,4'- At least one isocyanate monomer in the group consisting of MDI and TDI. The isocyanate monomer may be an unreacted isocyanate monomer remaining when the urethane prepolymer (a) is obtained, or may be added after the urethane prepolymer (a) is obtained. The polyisocyanate component (A) preferably has a number average molecular weight of 200 to 800, and more preferably has a number average molecular weight of 300 or more and 700 or less. Although the polyisocyanate component (A) contains the urethane prepolymer (a), it is preferred that the polyisocyanate component (A) exhibit a molecular weight as described above by containing an isocyanate monomer.

The polyisocyanate component (A) used in this embodiment preferably contains an isocyanate group in an amount of 10% by mass or more and less than 18% by mass. When the content of the isocyanate group of the polyisocyanate component (A) is within the above range, a laminated body having a better appearance can be formed even when a film substrate having a high gas barrier property is used. The content of the isocyanate group (% by mass) is determined by titration with hydrochloric acid as described later.

In addition, the respective ratios of 4,4'-MDI, 2,4'-MDI, and TDI contained in the polyisocyanate component (A) are preferably 4,4'-MDI, 2,4'-MDI, and TDI. Of the total 100 mol%, 4,4'-MDI is 30 mol% or more and 70 mol% or less, 2,4'-MDI is 30 mol% or more and 70 mol% or less, and TDI is 30 mol% Above 70%, below 70 mole%. With the composition ratio of the two MDIs in the above range, even if the aging temperature is not controlled to a temperature exceeding 40 ° C., the coating appearance of the ink portion in the laminated body is good, and good adhesion performance can be exhibited. When only 2,4'-MDI or TDI is used, short-term aging cannot exhibit sufficient adhesion performance. On the other hand, when only 4,4'-MDI is used, the appearance of the ink portion in the laminate is not sufficiently improved.

Next, the polyol component (B) contained in the adhesive composition in this embodiment is demonstrated. The polyol component (B) requires a polyester polyol having a number average molecular weight of 500 or more and 3,000 or less, and may further include a diol selected from a number average molecular weight of 50 or more and less than 500, a number average molecular weight of 50 or more, or less At least one of the group consisting of a triol of 500 and a polyether polyol having a number average molecular weight of 500 or more and 10,000 or less. By using a polyester polyol, sufficient adhesion strength can be obtained. It is further selected from the group consisting of a diol having a number average molecular weight of 50 or more and less than 500, a triol having a number average molecular weight of 50 or more and less than 500, and a polyether polyol having a number average molecular weight of 4,500 or more and 10,000 or less. At least one of the group can increase the intensity under high humidity.

A polyester polyol having a number average molecular weight of 500 or more and 3,000 or less as an essential component of the polyol component (B) will be described. Examples of the polyester polyol include a polycarboxylic acid such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, and sebacic acid, or a dialkyl ester or a mixture of these, and, for example, Ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3'-dimethylol Polyester polyols obtained by reacting heptane, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol and other diols or mixtures thereof, or polycaprolactone, polyvalerolactone, Polyester and the like obtained by ring-opening polymerization of lactones such as poly (β-methyl-γ-valerolactone). Furthermore, vegetable oils such as castor oil and polyester compounds derived from vegetable oils can also be used.

Representative examples of vegetable oils include hemp seed oil, linseed oil, perilla oil, Austrian oil, olive oil, cocoa oil, kapok oil, gardenia oil, mustard oil, almond oil, ketone oil, stone chestnut oil, Walnut oil, poppy oil, sesame oil, safflower oil, radish seed oil, soybean oil, daphnia oil, camellia oil, corn oil, rapeseed oil, soap factory oil, rice bran oil, palm oil, ramie oil, sunflower oil, grapes Seed oil, almond oil, pine seed oil, cottonseed oil, coconut oil, peanut oil, dehydrated ramie oil, etc.

A part of the hydroxyl groups in the obtained polyester diol and an acid anhydride such as trimellitic anhydride may be further reacted as a polyester diol. By using the polyester diol to which an acid anhydride is added, when it is applied to a sheet-like substrate that is difficult to adhere, the adhesiveness can be improved. The used amount of the added trimellitic anhydride and the like is preferably 0.1 to 5% by mass based on 100% by mass of the polyester diol after the reaction. By using a polyester polyol having a number-average molecular weight within the above range, compatibility with the polyisocyanate component (A) containing polyether polyurethane as an essential constituent component becomes good, and can be improved. A transparent adhesive composition was obtained, and sufficient adhesive performance was exhibited.

Examples of the diol having a number-average molecular weight of 50 or more and less than 500 include polyester diols, polyether diols, polyether ester diols, polyester amine diols, acrylic diols, and polycarbonate diols. Alcohol or ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3'-dihydroxyl Low-molecular-weight diols such as methylheptane and 2-methyl-1,3-propanediol or a mixture of these. From the viewpoint of reactivity, these compounds are preferably low-molecular-weight diols.

Examples of the polyether diol include an oxygen heterocycle such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran, using a difunctional low-volume polyol such as water, ethylene glycol, and propylene glycol as a starter. A polyether diol obtained by polymerizing a propane compound.

Examples of the polyetherester polyol include dibasic acids such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, and sebacic acid, or dialkyl esters or mixtures of these and A polyetherester polyol obtained by reacting the polyetherdiol.

The polyester amine diol can be obtained by combining, as a raw material, an aliphatic diamine having an amine group such as ethylenediamine, propylenediamine, and hexamethylenediamine during the esterification reaction. use.

As an example of an acrylic diol, it can be obtained by making hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or the like containing one or more hydroxyl groups in one molecule, or corresponding ones of these compounds. A methacrylic acid derivative or the like is copolymerized with, for example, acrylic acid, methacrylic acid, or an ester thereof.

Examples of the polycarbonate diol include those selected from ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 3-methyl- 1,5-pentanediol, 1,9-nonanediol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4- One obtained by reacting one or two or more diols in cyclohexanedimethanol with dimethyl carbonate, diphenyl carbonate, diethyl carbonate, phosgene and the like.

Examples of the triol having a number-average molecular weight of 50 or more and less than 500 include low-molecular-weight triols such as polyether triol, castor oil, trimethylolpropane, and glycerin, or mixtures thereof. From the viewpoint of reactivity, these are preferably low molecular triols or polyether triols.

Examples of the polyether triol include oxetane compounds such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran, using a low amount of triol such as trimethylolpropane and glycerin as a starter. Polyether triol obtained by polymerization.

Examples of the polyether polyol used as a polyether diol having a number average molecular weight of 500 or more and less than 10,000 include low molecular weight polyols such as water, ethylene glycol, propylene glycol, trimethylolpropane, and glycerin as a starting point. And a polyether polyol obtained by polymerizing an oxetane compound such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran.

The polyol component (B) preferably contains a polyester polyol having a number average molecular weight of 500 or more and 3,000 or less in 100% by mass of the polyol component (B), with a mass average molecular weight of 500 or more and 3,000 or less. Diols having a number average molecular weight of 50 or more and less than 500%, triols having a number average molecular weight of 50 or more and less than 500, and polyether polyols having a number average molecular weight of 4,500 or more and 10,000 or less. By combining the diol, triol, and polyether diol in the above-mentioned range, it is possible to obtain a high-speed coating and lamination using a film substrate with high gas barrier properties, and obtain A laminated body with a better appearance.

The polyol component (B) is in addition to the diol having a number average molecular weight of 50 or more and less than 500, a triol having a number average molecular weight of 50 or more and less than 500, and a polyether polyol having a number average molecular weight of 4,500 or more and 10,000 or less. Other than this, other polyol components can be included in the range which does not impair the objective of this embodiment.

When the number of mols of hydroxyl groups in the polyol component (B) is 100 mol, the adhesive composition in the present embodiment is preferably a mol of an isocyanate group in the polyisocyanate component (A). The number is 120 mol or more and 300 mol or less. When the molar number of hydroxyl groups in the polyol component (B) is set to 100 molar, the molar number of isocyanate groups in the polyisocyanate component (A) is within the above range, even under high humidity. Aging also shows good adhesion.

The adhesive composition in this embodiment is preferably one of 4,4'-MDI, 2,4'-MDI, and TDI contained in a total of 100% by mass of the polyisocyanate component (A) and the polyol component (B). The total amount is 10% to 34% by mass, and preferably 12% to 32% by mass. When the total amount of 4,4'-MDI, 2,4'-MDI, and TDI contained in 100% by mass of the total of the polyisocyanate component (A) and the polyol component (B) is within the above range, When a film substrate having a high gas barrier property is used, a laminated body having a better appearance can be obtained.

The adhesive composition in this embodiment may further include particles having an average particle diameter of 1 × 10 ^-4 mm or more and 4 × 10 ^-4 mm or less. By containing particles having an average particle diameter within the above range, when a film substrate having a high gas barrier property is used for coating and bonding at a high speed, a laminated body having a more external appearance can be obtained. If the particles are too small, even if added, the flow characteristics do not change much, so the appearance does not change much. Here, the average particle diameter is a volume average diameter, and is a value obtained by a laser light scattering method.

As the particles, any of an inorganic compound and an organic compound can be used, and these particles can be used alone or in combination of two or more.

Examples of the particles of the inorganic compound include alumina, aluminum silicate, aluminum hydroxide, alumina white, potassium sulfate, zinc oxide, zinc carbonate, magnesium aluminometasilicate, and silicic acid. Magnesium, magnesium oxide, magnesium carbonate, magnesium hydroxide, barium titanate, barium sulfate, barium carbonate, calcium carbonate, calcium hydroxide, calcium oxide, calcium silicate, calcium sulfite, calcium sulfate, titanium oxide, silica, zeolite , Activated carbon, kaolin, talc, pyrophyllite clay, silica, mica, graphite, sericite, montmorillonite, sericite, meerschaum, bentonite, perlite, zeolite, wollastonite, fluorite , Dolomite, etc. These prizes use silica or talc.

Examples of the particles of the organic compound include benzoguanamine resin, silicon-based resin, styrene resin, crosslinked polystyrene, epoxy resin, phenol resin, fluororesin, polyethylene resin, polyester resin, and polyfluorene. Imine resin, polyamide resin, polyacetal resin, polyurethane resin, vinyl acetate copolymer resin, polyphenylene oxide resin, nylon 6, nylon 12, cellulose, acrylic resin , Methacrylic resin, etc. Among these, benzoguanamine resin is used.

The content of the particles is preferably 0.01 to 10 parts by mass with an average particle diameter of 1 × 10 ^-4 mm or more based on 100 parts by mass of the total of the polyisocyanate component (A) and the polyol component (B). Particles (C) below 4 × 10 ^-4 mm. By being in this range, the appearance and adhesion strength can be improved in a well-balanced manner.

The particles may be mixed with the polyisocyanate component (A) and the polyol component (B) at the same time, or may be mixed in advance with any one of the components and then mixed with the other component. The particles are preferably mixed in advance with the polyol component (B) component.

The adhesive composition in this embodiment is preferably free of a solvent, and is preferably prepared at a temperature as low as possible within a range that can ensure fluidity. Specifically, it is preferably 25 ° C or higher, Blend below 80 ° C. The viscosity at 60 ° C. immediately after mixing the polyisocyanate component (A) and the polyol component (B) is preferably 50 mPa · s or more, 5000 mPa · s or less, and more preferably 50 mPa · s or more, 3000 mPa · s or less. In addition, in the present embodiment, "just after mixing" means that within 1 minute after uniform mixing, and the melt viscosity indicates a value obtained by a B-type viscometer. If the melt viscosity at 60 ° C exceeds 5,000 mPa · s, it will be difficult to apply and it will be difficult to ensure good workability. If the application temperature is 60 ° C or lower, a good coating appearance may not be obtained. On the other hand, if the melt viscosity at 60 ° C is less than 50 mPa · s, there is a tendency that the initial cohesive force is weak, and therefore sufficient adhesion performance cannot be obtained. When the adhesive composition is applied to a substrate, the thickness of the coating film is not large. It becomes uniform and produces a poor appearance or warping.

The adhesive composition in this embodiment can further use additives such as antioxidants, ultraviolet absorbers, hydrolysis inhibitors, mold inhibitors, tackifiers, plasticizers, defoamers, pigments, and fillers as needed. Further, in order to further improve the bonding performance, a bonding aid such as a silane coupling agent, phosphoric acid, a phosphoric acid derivative, an acid anhydride, and an adhesive resin can be used. In order to adjust the curing reaction, a known catalyst, an additive, or the like can be used.

As the silane coupling agent, a functional group such as a vinyl group, an epoxy group, an amine group, an imino group, or a mercapto group and a functional group such as a methoxy group or an ethoxy group can be used. Examples include chlorosilanes such as vinyltrichlorosilane, aminosilane such as N- (dimethoxymethylsilylpropyl) ethylenediamine, and N- (triethoxysilylpropyl) ethylenediamine, Epoxy silanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, vinyl silanes such as vinyltriethoxysilane and the like. The addition amount of the silane coupling agent is preferably from 0.1% by mass to 5% by mass with respect to all the adhesive composition.

Among the phosphorus oxyacids or derivatives thereof used in the present embodiment, any one having at least one free oxo acid as the phosphorus oxyacid may be used, and for example, hypophosphite is mentioned. , Phosphorous acids such as phosphorous acid, orthophosphoric acid, hypophosphorous acid, and condensed phosphoric acids such as metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid, and superphosphoric acid. In addition, examples of the phosphorus oxo acid derivative include those obtained by partially esterifying the phosphorus oxo acid with alcohols while leaving at least one or more free oxo acids. Examples of the alcohols include aliphatic alcohols such as methanol, ethanol, ethylene glycol, and glycerol, and aromatic alcohols such as phenol, xylenol, hydroquinone, catechol, and resorcinol. As the phosphorus oxyacid or a derivative thereof, one kind or two or more kinds can be used. The addition amount of phosphorus oxyacid or its derivative is 0.01% to 10% by mass, preferably 0.05% to 5% by mass, and more preferably 0.1% to 1% by mass based on the total composition. .

<Laminated body and its manufacturing method> The laminated body and its manufacturing method of this embodiment are demonstrated. As described above, the laminated body of the embodiment includes the first substrate, the ink layer, the adhesive layer, and the second substrate in this order.

Examples of the first substrate include polyolefins such as polyethylene and polypropylene, polyethylene terephthalate (hereinafter also referred to as PET), polyesters such as polycarbonate and polylactic acid, polystyrene, AS resin, Polystyrene resins such as ABS resin, nylon, polyamide, polyvinyl chloride, polyvinylidene chloride, cellophane, paper, aluminum, etc., or films or sheets of composite materials containing these are used The printing method is applied and fixed by drying or curing in an oven to obtain a printed matter. The substrate may be subjected to a vapor deposition coating treatment and / or a polyvinyl alcohol coating treatment on the surface of a metal oxide or the like, or may be further subjected to a surface treatment such as a corona treatment.

The ink layer is a dried or hardened product of the ink composition containing a specific polyurethane polyurea resin and a specific amount of a vinyl chloride-vinyl acetate copolymer. The ink layer can be obtained by printing or drying the ink composition on the first substrate. The ink composition can be printed by a known printing method such as gravure printing or flexographic printing, and is more preferably printed by a gravure printing method. As the cylinder used in gravure printing, a known type such as a engraving type or an etching type is used. The ink composition diluted to a viscosity and concentration suitable for gravure printing with a diluting solvent is supplied to each printing unit individually or after mixing, and after printing, it is dried or hardened in an oven to form an ink layer. The temperature of the oven is usually 40 ° C to 80 ° C, and the printing speed is usually 50 m / minute to 300 m / minute. The ink layer is usually 0.5 g / m ² to 5 g / m ² , and preferably 1 g / m ² to 3.5 g / m ² .

As described above, the adhesive layer is such that the total amount of 4,4'-MDI, 2,4'-MDI, and TDI contained in 100% by mass of the total of the polyisocyanate component (A) and the polyol (B) becomes 10 The cured product of the adhesive composition obtained by mixing the specific polyisocyanate component (A) and the specific polyol component (B) as a mass% to 34 mass% can be obtained, for example, by the following method. That is, the adhesive composition is coated on the ink layer or on a second substrate having an oxygen permeability at 25 ° C of 100 cc / (m ² · day · atm) or less to form an adhesive layer. Precursor. The coating amount of the adhesive composition can be appropriately selected according to the type of the second substrate, the coating conditions, etc., and is usually 1 g / m ² to 5 g / m ² , and preferably 1.5 g / m ² to 4.5 g. / m ² . Thereafter, a second substrate having an oxygen permeability at 25 ° C of 100 cc / (m ² · day · atm) or less is superposed on the precursor of the adhesive layer, or an ink layer, that is, is provided on the first substrate. The non-contact surface of the white ink layer on the first substrate overlaps the precursor of the adhesive layer, and then aging under normal temperature or heating to harden the precursor to make an adhesive layer. And manufacture laminated body. In the case of the adhesive composition in this embodiment, the time required for aging is about one day. Moreover, in the case of the adhesive composition in this embodiment, even if the environmental humidity from the time of application to aging is high, sufficient adhesive performance can be exhibited.

(Second substrate) The second substrate used had an oxygen permeability at 25 ° C of 100 cc / (m ² · day · atm) or less. The oxygen transmission is affected by the thickness. In this application, based on the average oxygen transmission rate (hereinafter referred to as the oxygen transmission coefficient) and thickness per unit thickness (1 μm), the oxygen transmission rate below 100 cc / (m ² · day · atm) can be used as Second substrate. The temperature of the oxygen permeability and the oxygen permeability coefficient means a value at 25 ° C unless otherwise specified. For example, since an ethylene-vinyl alcohol copolymer having an ethylene content of 56% has an oxygen transmission coefficient of 3 cc / (m ² · day · atm), 1 μm may be used. On the other hand, a plastic film having a large oxygen transmission coefficient as shown below can also be used depending on the film thickness. That is, an acrylonitrile copolymer having an acrylonitrile content of 70% has an oxygen transmission coefficient of 300 cc / (m ² · day · atm). Therefore, if the film thickness is 3 μm or more, it can be used. Similarly, if a vinylidene chloride copolymer having an oxygen transmission coefficient of 400 cc / (m ² · day · atm) is set to a film thickness of 4 μm or more, it can be used as a second substrate. If the oxygen transmission coefficient is 1700 cc / (m ² · day · atm) nylon 6 with a film thickness of 17 μm or more can be used as the second substrate. If the oxygen transmission coefficient is 1925 cc / (m ² · day · atm) nylon 66 can be used as a second substrate with a film thickness of 19.25 μm or more, and a polyethylene terephthalate with an oxygen transmission coefficient of 768 cc / (m ² · day · atm) can be used as a film thickness of 7.68 μm Above, it can be used as a second substrate. If the terephthalic acid-bisphenol copolymer polyacrylate having an oxygen transmission coefficient of 2580 cc / (m ² · day · atm) is set to a film thickness of 25.8 μm or more, Can be used as a second substrate. If polyacetal with an oxygen transmission coefficient of 4850 cc / (m ² · day · atm) is set to a film thickness of 48.5 μm or more, it can be used as a second substrate. Polychlorotrifluoroethylene with a coefficient of 650 cc / (m ² · day · atm) can be used as a second substrate with a film thickness of 6.5 μm or more. If the oxygen transmission coefficient is 1300 cc / (m ² · day · Atm) of polyvinylidene fluoride To a thickness of more than 13 μm, it is used as the second substrate.

In addition, a vapor-deposited film obtained by vapor-depositing aluminum, silicon oxide, aluminum oxide, or the like into various plastic films can also be used as the second substrate. In most cases, the thickness of the vapor deposition layer is about 1 nm to 500 nm. By providing such a vapor deposition layer, the influence of the type and thickness of the plastic film on the oxygen permeability is very small. For example, an aluminum vapor-deposited layer provided on an unstretched polypropylene film has an oxygen permeability of 20 cc / (m ² · day · atm) to 10 cc / (m ² · day · atm) and is used as the second The substrate has an oxygen transmission rate of 2 cc / (m ² · day · atm) to 0.3 cc / (m ² · day · atm) when an aluminum vapor-deposited layer is provided on a polyethylene terephthalate film. As a second substrate, the oxygen transmission rate of an aluminum oxide vapor deposition layer on a polyethylene terephthalate film is 4 cc / (m ² · day · atm) to 0.5 cc / (m ² · Day · atm), and used as a second substrate, the oxygen transmission rate of a silicon oxide vapor-deposited layer on a polyethylene terephthalate film was 5 cc / (m ² · day · atm) ~ 0.3 cc / (m ² · day · atm), and used as the second substrate. In addition, as the metal foil, regardless of the thickness, metal foils such as stainless steel, iron, copper, and lead have an oxygen permeability of 0 cc / (m ² · day · atm). As the second base material, those having a vapor-deposited layer or metal foil on various plastic films are preferred, and those having a metal-deposited metal film on various plastic films (hereinafter, sometimes referred to as a vapor-deposited film) are preferred. In addition, it is preferable that the metal vapor-deposited layer is in contact with the adhesive layer. As a more preferable aspect, as a preferable aspect of the second substrate, there is a state in which a transparent film and a metal vapor-deposited layer on one main surface of the transparent film are laminated.

The oxygen transmission rate can be determined using an oxygen transmission rate measuring device in accordance with the method of JISK 7126. For example, the MOCON oxygen transmission rate measuring device (OX-TRAN2 / 21) manufactured by Hitachi High-Tech Science Co., Ltd. is a Coulomb that has a carrier gas (nitrogen) that generates a current proportional to the amount of oxygen passing through the sample. The device of the sensor measures the change in voltage with a standard load resistance and converts it to oxygen permeability. [Example]

Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to the following examples. Unless otherwise specified, the percentages and parts in the examples are based on quality.

<Method for measuring mass average molecular weight (Mw) and number average molecular weight (Mn)> The mass average molecular weight (Mw) and number average molecular weight (Mn) are measured using GPC (gel permeation chromatography) manufactured by Showa Denko Corporation. Showa GPC System (Shodex GPC System) -21 ". GPC is a liquid chromatography method for separating and quantifying a substance dissolved in a solvent based on a difference in molecular size. Tetrahydrofuran is used as a solvent and the molecular weight is determined in terms of polystyrene.

<Measurement method of hydroxyl value> About 1 g of a sample was accurately measured in a conical flask, and 100 mL of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution was added to dissolve. Furthermore, 5 mL of an acetamating agent was accurately added (25 g of acetic anhydride was dissolved with pyridine to make a solution with a capacity of 100 mL), and stirred for about 1 hour. A phenolphthalein test solution was added thereto as an indicator for 30 seconds. Thereafter, titration was performed with a 0.1 N alcoholic potassium hydroxide solution until the solution showed a pale red color. The hydroxyl value is determined by the following (Formula 1). The hydroxyl value is a numerical value (unit: mgKOH / g) of the dry state of the resin. (Formula 1) Hydroxyl value (mgKOH / g) = [{(ba) × F × 28.25} / S] / (non-volatile concentration / 100) + D where S: sample amount (g) a: 0.1 Consumption of N alcoholic potassium hydroxide solution (mL) b: Consumption of 0.1 N alcoholic potassium hydroxide solution in blank experiment (mL) F: 0.1 Valence of N alcoholic potassium hydroxide solution D: Acid value ( mgKOH / g)

<Measurement method of acid value> An approximately 1 g sample was accurately measured in a conical flask, and 100 mL of a toluene / ethanol (capacity ratio: toluene / ethanol = 2/1) mixed solution was added to dissolve. A phenolphthalein test solution was added as an indicator, and after maintaining for 30 seconds, a 0.1 N alcoholic potassium hydroxide solution was added dropwise until the solution showed a light red color. The acid value is obtained by the following (Formula 2). The acid value is a numerical value (unit: mgKOH / g) of the dry state of the resin. (Formula 2) Acid value (mgKOH / g) = [{5.611 × a × F} / S] (non-volatile concentration / 100) where S: sample amount (g) a: 0.1 N alcoholic hydroxide Consumption of potassium solution (mL) F: Force value of 0.1 N alcoholic potassium hydroxide solution

<Measurement method of NCO content (mass%)> A 200-mL Erlenmeyer flask accurately weighs about 1 g of a sample, and 10 mL of 0.5 N di-n-butylamine (toluene solution), 10 mL of toluene was used for dissolution. A phenolphthalein test solution was added thereto as an indicator, and after maintaining for 30 seconds, a 0.25 N hydrochloric acid solution was added dropwise until the solution showed a light red color. NCO (mass%) can be calculated | required by following (Equation 3). (Formula 3) NCO (mass%) = {(ba) × 4.202 × F × 0.25} / S where S: sample amount (g) a: consumption of 0.25 N hydrochloric acid solution (mL) b: blank Consumption of experimental 0.25 N hydrochloric acid solution (mL) F: Force value of 0.25 N hydrochloric acid solution

(Synthesis of Polyurethane Polyurea Resin for Ink Composition) [Synthesis Example 1-1] In a four-necked flask equipped with a stirrer, a thermometer, a reflux cooler, and a nitrogen introduction tube, 11.17 parts of a polyester polyol was charged. A1 (Kuraray Polyol P-2010, copolymer of 3-methyl-1,5 pentanediol and adipic acid, number average molecular weight 2000, manufactured by Kuraray), 11.17 parts polymer Ether Polyol B1 (EXCENOL 2020, polymer of propylene oxide, number average molecular weight 2000, manufactured by Asahi Glass Co., Ltd.), 5.34 parts of isophoric diisocyanate (hereinafter also referred to as IPDI), 4.36 parts of ethyl acetate Ester, 0.003 parts of tin 2-ethylhexanoate, reacted at 90 ° C for 5 hours under a nitrogen gas stream, and added 7.5 parts of ethyl acetate and cooled to obtain a urethane prepolymer having an isocyanate group at the terminal The solution. Then, 1.97 parts of isophorone diamine (hereinafter also referred to as IPDA), 0.2 parts of 2-hydroxyethyl ethylenediamine, 0.33 parts of di-n-butylamine, 30.13 parts of ethyl acetate, and 28 parts of isopropyl In a mixture of propanol (hereinafter also abbreviated as IPA), a solution of the obtained urethane prepolymer was slowly added at room temperature, followed by a reaction at 50 ° C for 1 hour to obtain a solid content of 30. % Polyurethane polyurea resin solution (PU1) with a mass average molecular weight of 15,000. In this synthesis example, a solution of the obtained urethane prepolymer was added dropwise to amines to perform a chain extension reaction.

[Synthesis Example 1-2] A polyurethane polyurea resin solution (PU2) was obtained in the same manner as in Synthesis Example 1-1 using the feed ratios in Table 1.

[Synthesis Example 1-3] In a four-necked flask equipped with a stirrer, a thermometer, a reflux cooler, and a nitrogen introduction tube, 11.21 parts of polyester polyol A1, 11.21 parts of polyether polyol B1, 5.36 parts of IPDI, and 4.36 parts of acetic acid were charged. Ethyl acetate, 0.003 parts of tin 2-ethylhexanoate, reacted at 90 ° C for 5 hours under a nitrogen stream, and added 7.5 parts of ethyl acetate and cooled to obtain a urethane prepolymer having an isocyanate group at the terminal Of the solution. Then, 1.87 parts of IPDA, 0.2 parts of 2-hydroxyethylethylenediamine, 0.17 parts of di-n-butylamine, and 30.13 parts of the solution of the obtained urethane prepolymer were slowly added at room temperature. A mixture of ethyl acetate and 28 parts of IPA. Next, it reacted at 50 degreeC for 1 hour, and obtained the polyurethane polyurea resin solution (PU3) of 30% of solid content and 50000 mass average molecular weight. In this synthesis example, amines were added dropwise to the solution of the obtained urethane prepolymer to perform a chain extension reaction.

[Synthesis Example 1-4 to Synthesis Example 1-8] Polyurethane polyurea resin solutions (PU4 to PU8) were obtained in the same manner as in Synthesis Example 1-1 using the feed ratios in Table 1. The polyester polyol A2 and the polyether polyol B2 are as follows. Polyester polyol A2: Kuraray polyol P-5010, a copolymer of 3-methyl-1,5-pentanediol and adipic acid, a number average molecular weight of 5,000, manufactured by Kuraray Company. Polyether polyol B2: EXCENOL 420, a polymer of propylene oxide, a number average molecular weight of 400, manufactured by Asahi Glass Co., Ltd.

[Synthesis Example 1-9 to Synthesis Example 1-13] Polyurethane polyurea resin solutions (PU9 to PU13) were obtained in the same manner as in Synthesis Example 1-1 using the feed ratios in Table 2.

[Table 1]

[Table 2]

(Adjustment of Ink Composition) [Production Example 1] 5 parts of a polyurethane polyurea resin solution (PU1), 5 parts of a vinyl chloride-vinyl acetate copolymer solution C1 (Solbin TA5R, Manufactured by Nissin Chemical Industry Co., Ltd., diluted with vinyl acetate, solid content is 30% by mass), 30 parts of titanium oxide (TITONE R45M, manufactured by Sakai Chemical Co., Ltd.), 10 parts of ethyl acetate / IPA mixed solvent (mass (75/25 ratio). After mixing with a sand mill, 32.5 parts of polyurethane polyurea resin solution (PU1), 7.5 parts of vinyl chloride-vinyl acetate copolymer solution C1, and 10 parts of acetic acid were added. Ethyl / IPA mixed solution (mass ratio 75/25), after stirring and mixing, dilute with a mixed solvent of methyl ethyl ketone, n-propyl acetate, and IPA (mass ratio 40:40:20), and use Cai Zahn Cup # 3 (manufactured by Clutch) was adjusted for 15 seconds to obtain an ink composition (i-1).

[Production Example 2 to Production Example 22] The ink compositions (i-2 to i-22) were obtained by the same methods as in Production Example 1-1 using the feed ratios in Tables 3 and 4. As the pigment, in addition to titanium oxide, C.I. Pigment Yellow 83, which is a yellow pigment, may be used. Furthermore, as the resin other than the polyurethane polyurea resin solution and the vinyl chloride-vinyl acetate copolymer solution C1, the following resins were all diluted with ethyl acetate to a solid content of 30% by mass. Resin solution. Vinyl chloride-vinyl acetate copolymer solution C2 (Solbin CL, manufactured by Nissin Chemical Industry Co., Ltd.) Vinyl chloride-vinyl acetate copolymer solution C3 (Solbin AL, Nissin Chemical Industry Co., Ltd.) Manufacturing) Nitrocellulose solution (DLX5-8, manufactured by Nobel Enterprises)

[table 3]

[Table 4]

Synthesis of Polyisocyanate Component (A) for Adhesive Composition (Synthesis Example 101) 300 parts of polypropylene glycol (hereinafter referred to as PPG-400) having a number average molecular weight of about 400, and 400 parts of polypropylene glycol having a number average molecular weight of about 2000 ( Hereinafter, it is referred to as PPG-2000), 200 parts of triol (hereinafter referred to as PPG-400-trifunctional) having a number average molecular weight of 400 added to glycerol in glycerol, 400 parts of 4,4'-MDI and 600 Portions of 2,4'-MDI were put into the reaction vessel. In addition, the urethane reaction was carried out by heating at 70 ° C to 80 ° C for 3 hours while stirring under a nitrogen gas flow, and an isocyanate group content rate of 14.4% and an MDI monomer content rate of 33% were obtained. Isocyanate-based polyether polyurethane polyisocyanate resin. Hereinafter, this resin is referred to as polyisocyanate A1- (1).

(Synthesis example 102 to synthesis example 103) According to the composition shown in Table 5, it carried out similarly to the synthesis example 1, and obtained polyisocyanate A1- (2) and polyisocyanate which are polyether polyurethane polyisocyanate resin. A1- (3).

(Synthesis Example 104) 80 parts of isophthalic acid, 460 parts of adipic acid, 60 parts of 1,6-hexanediol, and 400 parts of diethylene glycol were put into a reaction vessel, and they were heated while being stirred under a stream of nitrogen. The esterification reaction is performed at 150 ° C to 240 ° C. When the acid value is 1.3 (mgKOH / g), the reaction temperature is set to 200 ° C, the inside of the reaction vessel is gradually depressurized, and the reaction is performed at 1.3 kPa or less for 30 minutes to obtain an acid value of 0.4 (mgKOH / g), Polyester polyol 1 having a hydroxyl value of 80 (mgKOH / g) and a number average molecular weight of about 1400 having hydroxyl groups at both ends. 150 parts of the obtained polyester resin, 190 parts of PPG-400, 310 parts of 4,4'-MDI, and 350 parts of 2,4-MDI were put into a reaction vessel, and stirred under a nitrogen stream at 70 ° C to 80 The urethanization reaction was performed by heating at 3 ° C for 3 hours to obtain a polyether polyurethane polyisocyanate resin having an isocyanate group having an isocyanate group content of 17% and an MDI monomer content of 48%. Hereinafter, this resin is referred to as polyisocyanate A1- (4).

(Synthesis Example 105) 200 parts of PPG-400, 200 parts of castor oil, and 145 parts of TDI were put into a reaction vessel, and the mixture was stirred under a nitrogen stream while heating at 80 ° C for 1 hour to form a urethane. After the reaction, 178 parts of 4,4'-MDI and 192 parts of 2,4-MDI were added, and the mixture was stirred under a nitrogen stream while heating at 80 ° C for 3 hours to perform a urethane reaction to obtain an isocyanate group. A polyether polyurethane polyisocyanate resin having an isocyanate group and a content ratio of 16.1% and an MDI monomer and a TDI monomer content of 37%. Hereinafter, this resin is referred to as polyisocyanate A1- (5).

(Synthesis Example 106) 208 parts of adipic acid and 192 parts of diethylene glycol were put into a reaction vessel, and the mixture was heated to 150 ° C. to 240 ° C. while being stirred under a nitrogen gas stream to perform an esterification reaction. When the acid value is 1.3 (mgKOH / g), the reaction temperature is set to 200 ° C, the inside of the reaction vessel is gradually depressurized, and the reaction is performed at 1.3 kPa or less for 30 minutes to obtain an acid value of 0.5 (mgKOH / g), Polyester polyol 2 having a hydroxyl value of 56.1 (mgKOH / g) and a number average molecular weight of about 2000 and having hydroxyl groups at both ends. 70 parts of the obtained polyester resin, 367 parts of PPG-400, and 265 parts of TDI were put into a reaction vessel, and the mixture was stirred under a nitrogen stream while heating at 80 ° C for 1 hour to perform a urethane reaction 286 parts of 4,4'-MDI were added, and the mixture was stirred under a nitrogen stream while heating at 80 ° C for 3 hours to carry out a urethanization reaction. The isocyanate group content was 12%, the MDI monomer and A polyether polyurethane polyisocyanate resin having an isocyanate group with a TDI monomer content of 27%. Hereinafter, this resin is referred to as polyisocyanate A1- (6).

(Synthesis Example 107) 300 parts of PPG-400, 200 parts of PPG-2000, 480 parts of 4,4'-MDI, and 320 parts of 2,4-MDI were put into a reaction vessel, and stirred under a nitrogen gas stream at 80 The urethane was reacted by heating at 3 ° C for 3 hours to obtain a polyether polyurethane polyisocyanate resin having an isocyanate group having an isocyanate group content of 15.4% and an MDI monomer content of 34%. Hereinafter, this resin is referred to as polyisocyanate A1- (7).

(Synthesis Example 108) 300 parts of PPG-400, 400 parts of PPG-2000, 200 parts of PPG-400-trifunctional, and 1,000 parts of 4,4'-MDI were put into a reaction vessel and stirred under a nitrogen gas stream while Polyurethane polyisocyanate resin with isocyanate group was obtained by heating at 80 ° C for 3 hours to carry out a urethane reaction to obtain an isocyanate group content of 14.4% and an MDI monomer content of 33% . Hereinafter, this resin is referred to as polyisocyanate A1- (8).

(Synthesis Example 109) 607 g of xylylene diisocyanate (hereinafter referred to as XDI) and 672 g of butene adipic acid with a molecular weight of about 1,000 that exhibit crystallinity at room temperature (manufactured by Takeda Pharmaceutical Industry Co., Ltd., Takrak (Takelac) U-2410), 118 g of diethylene glycol, 156 g of trifunctional polypropylene glycol (manufactured by Takeda Pharmaceutical Industry Co., Ltd., Actcall 32-160, hereinafter referred to as PPG-1000) (Functional), 0.6 g of benzamidine chloride were respectively put into the reactor, and the carbamate reaction was performed under a nitrogen gas flow at 70 ° C to 80 ° C. After the reaction was completed, 389 g of an aliphatic polyisocyanate was added. Polymer modified polyisocyanate (manufactured by Takeda Pharmaceutical Co., Ltd., Takelac D-170NH, hereinafter also referred to as HDI trimer), uniformly mixed under a nitrogen stream at 70 ° C to 80 ° C A polyisocyanate component having an isocyanate group content of 6.3%, an XDI monomer (NCO monomer) content of 13%, and an MDI monomer content of 0% was obtained. Hereinafter, this resin is referred to as polyisocyanate A1- (9).

[table 5]

Synthesis of Polyol Component (B) for Adhesive Composition (Synthesis Example 201) 115 parts of isophthalic acid (hereinafter referred to as IPA), 304 parts of adipic acid (hereinafter referred to as ADA), and 305 parts of diethylene glycol (Hereinafter referred to as DEG), 75 parts of neopentyl glycol (hereinafter referred to as NPG) were put into a reaction vessel, and the mixture was heated to 150 ° C. to 240 ° C. while being stirred under a nitrogen gas stream to perform an esterification reaction. When the acid value is 1.3 (mgKOH / g), the reaction temperature is set to 200 ° C, the inside of the reaction vessel is gradually depressurized, and the reaction is performed at 1.3 kPa or less for 30 minutes to obtain an acid value of 0.4 (mgKOH / g), A polyester diol resin having a hydroxyl value of 137 (mgKOH / g) and a number average molecular weight of about 800 having hydroxyl groups at both ends. Hereinafter, this polyol is referred to as polyester diol (b1) -1.

(Synthesis example 202 to synthesis example 207) According to the composition shown in Table 6, it carried out similarly to the synthesis example 201, and obtained the polyester diol (b1) -2-polyester diol (b1) -7.

(Preparation Example 301) 92 parts of the polyester diol (b1) -1 obtained in Synthesis Example 201 and 8 parts of diethylene glycol were mixed to obtain a polyol component B- (1).

(Preparation example 302 to preparation example 317) According to the composition shown in Table 7, it carried out similarly to preparation example 301, and obtained the polyol component B- (2) -polyol component B- (10).

[TABLE 6]

[TABLE 7]

(Production Example 401) 100 parts of the polyisocyanate component A1- (1) obtained in Synthesis Example 101 and 50 parts of the polyol component B- (1) obtained in Preparation Example 301 were mixed at 60 ° C to obtain a solvent-free type Adhesive composition AD1. In addition, the solventless adhesive composition AD1 contains 182 mol of isocyanate groups derived from the polyisocyanate component A1- (1) with respect to 100 mol hydroxyl groups in the polyol component. The amount of isocyanate groups with respect to 100 moles of hydroxyl groups can be determined as described below. Amount of isocyanate group with respect to 100 moles of hydroxyl group = [isocyanate group (eq.) / Hydroxyl group (eq.)] × 100 isocyanate group (eq.) = NCO content rate (% by mass) / (42 × 100) hydroxyl group (eq. .) = Hydroxyl value / 56100

In addition, the total ratio of 4,4'-MDI, 2,4'-MDI, 2,2'-MDI, and TDI (hereinafter referred to as isocyanate monomer) contained in 100% of the solventless adhesive composition. It's 22%. The isocyanate monomer content is the total area of the peak area of the MDI monomer derived from the vicinity of Mn = 200 to 300 and the peak area of the TDI monomer derived from the vicinity of Mn = 100 to 200 observed on the GPC chart divided by the GPC chart. Total area of all peaks observed above. Isocyanate monomer content (%) = (total peak area of isocyanate monomer / total area of all peaks) × 100

(Manufacturing example 402 to manufacturing example 416) According to the composition shown in Table 8, it carried out similarly to manufacturing example 401, and obtained the adhesive composition AD2-the adhesive composition AD16.

[TABLE 8]

[Example 1 to Example 13], [Comparative Example 1 to Comparative Example 9] [Production of printed matter] Using a gravure printing machine having a gravure having a plate depth of 30 μm, Production Example 1 to Production Example were performed at a printing speed of 50 m / min. The ink composition i-1 to ink composition i-22 obtained in 22 are printed on a corona-treated PET film (Toyobo E5100 # 12) as a first substrate, and dried in a 60 ° C oven or It hardens and forms an ink layer on the PET film.

[Production of laminated body] Using a solvent-free experimental coater, the solvent-free adhesive composition AD1 obtained in Production Example 401 was applied at a coating speed of 200 m / min at a temperature of 60 ° C (application amount: 2 g / m ² ) On the surface of the ink layer printed on the PET film, an aluminum-evaporated unstretched polypropylene film (hereinafter referred to as VMCPP) having an oxygen permeability of 20 cc / (m ² · day · atm) was deposited. Thickness: 25 μm) A vapor-deposited surface was superimposed on the coated surface to obtain a laminated body (pre-laminated body) in a preparation stage. These pre-laminated bodies were aged for one day in an environment of 25 ° C. and 80% RH, and the adhesive layer was hardened to produce a laminated body. About the obtained laminated body, the adhesive force of the laminated body and the interface state of the laminated body were evaluated by the following method. The results are shown in Table 9.

(Adhesive force) The laminated body was cut out into a test piece having a length of 300 mm and a width of 15 mm. Using an Instron tensile tester, the T-peel between PET / VMCPP was measured at a peeling speed of 300 mm / min at a temperature of 25 ° C and a peeling speed of 300 mm / min. Intensity (N). This test was performed five times, and the average value was calculated | required and it evaluated based on the following criteria. 5: Adhesive force 1.5 N or more 4: Adhesive force 1.0 N or more and less than 1.5 N 3: Adhesive force 0.6 N or more and less than 1.0 N 2: Adhesive force 0.3 N or more and less than 0.6 N 1: Adhesive force less than 0.3 N

(Interfacial State of the Laminated Body) The vapor deposition portion was visually observed through the ink layer and the adhesive layer from the first substrate side, and was evaluated by the following criteria. 5: No orange peel-like pattern or small spot-like pattern was observed in the vapor deposition portion. 4: No small speckle-like pattern was observed in the vapor deposition portion, but a small amount of orange peel-like pattern was observed. For use without problem. 3: Small spot-like patterns were not observed in the vapor deposition portion, but a large number of orange peel-like patterns were observed. For use without problem. 2: Not only a small amount of orange peel-like patterns but also a small number of small speckle-like patterns were observed on the vapor-deposited surface. 1: Not only a large number of orange peel-like patterns but also a large number of small speckle-like patterns were observed on the vapor-deposited surface.

[TABLE 9]

As shown in Table 9, it can be seen that Examples 1 to 13 in which an ink layer was formed using the ink composition in this example were excellent in appearance and adhesion after aging at 25 ° C for one day. In contrast, the polyurethane polyurea resin of Comparative Example 1 has a low molecular weight, insufficient cohesion of the ink layer, and particularly poor adhesion strength. Comparative Example 2 was not able to form a high molecular weight, uniform ink layer of a polyurethane polyurea resin, so the appearance of the laminate was poor. In Comparative Example 3, since the ratio of the polyester polyol in the polymer polyol having a number average molecular weight of 400 to 5000 in the polyurethane polyurea resin was low, the isocyanate monomer in the adhesive composition was easy to penetrate. In the ink layer, the adhesion is also poor, and the appearance of the laminate is also poor, especially the appearance of the laminate. In Comparative Example 4, the total concentration of the urethane bond and the urea bond in the polyurethane polyurea resin was low, and the isocyanate monomer in the adhesive composition easily penetrated into the ink layer, and the adhesive force and buildup Body appearance is poor. In Comparative Example 5, since the total concentration of the urethane bond and the urea bond in the polyurethane polyurea resin in the ink layer was higher than 2.4 mmol / g, a uniform ink layer could not be formed, and thus the appearance of the laminated body difference. In addition, since the adhesion of the ink layer to the transparent substrate tends to decrease, the adhesion force is also low. In Comparative Examples 6 and 7, the ink composition did not contain vinyl chloride-vinyl acetate copolymer at all, and the total of the polyurethane polyurea resin and vinyl chloride-vinyl acetate copolymer in Comparative Example 8 was 100. The vinyl chloride-vinyl acetate copolymer is contained in the proportion of 5% by mass. In Comparative Examples 6 to 8, since the chemical resistance derived from the vinyl chloride-vinyl acetate copolymer in the ink layer was significantly inferior, as in Comparative Examples 3 and 4, the isocyanate monomer in the adhesive composition was the same. The body is soaked in the ink layer, and the appearance and adhesion of the laminated body are poor. In Comparative Example 9, since the vinyl chloride-vinyl acetate copolymer exceeded the range of 5% to 40%, the adhesion of the ink layer to the transparent substrate was reduced, and the adhesion was particularly poor.

[Example 14 to Example 24], [Comparative Example 10 to Comparative Example 13] As shown in Table 10, except that i-2 was used instead of the ink composition i-1, those obtained in Manufacturing Example 402 to Manufacturing Example 416 were used. Except that the solventless adhesive composition AD2 to AD16 were used instead of the adhesive composition AD1, the same operation as in Example 1 was performed to obtain a laminate, and evaluation was performed in the same manner. The results are shown in Table 10.

[TABLE 10]

As shown in Table 10, it can be seen that Examples 14 to 24 in which an adhesive layer was formed using the adhesive composition in this example were excellent in appearance and adhesion after aging at 25 ° C for one day. In contrast, Comparative Example 10 uses an isocyanate component A1- (8) containing a urethane prepolymer (a) and 4,4'-MDI obtained using only 4,4'-MDI as an isocyanate component ( A). Therefore, the reaction speed is too fast, and the leveling property of the adhesive layer in the middle of hardening is reduced, so the appearance is not sufficient. Comparative Example 11 uses a polyester polyol B- (9) having a mass average molecular weight of 4000 as the polyol component (B). Therefore, the reactivity with the coated isocyanate component (A) decreases, and 4,4'- The ink film is damaged by the penetration of the isocyanate monomer, such as MDI, into the ink layer, and thus the appearance becomes poor. Comparative Example 12 used polyester polyol B- (10) having a mass average molecular weight of 300 as the polyol component (B), so the reaction rate with the isocyanate component (A) was too fast, and the leveling property of the adhesive layer in the middle of hardening Falling, so the appearance is not sufficient. Comparative Example 13 used an isocyanate component A1- (9) component derived from XDI and HDI as the isocyanate component (A), and the curing rate was slow. Therefore, the strength after aging at 25 ° C for one day was insufficient.

[Example 25 to Example 36], [Comparative Example 14 to Comparative Example 22] As shown in Table 11, except that the solventless adhesive composition AD10 obtained in Production Example 410 was used instead of the adhesive composition AD1, A laminated body was obtained in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The results are shown in Table 11.

[表 11] Table 11

According to Table 11, even if the adhesive composition was changed, the same tendency as in the case of Table 9 was confirmed. [Industrial availability]

The laminated body of the present invention can be applied to all laminated bodies having an ink layer. It is particularly useful for packaging materials such as food, clothing, and cosmetics.

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Claims (5)

A laminated body comprising a first substrate having visible light transmittance, an ink layer, an adhesive layer, and a second substrate having an oxygen transmission rate of 100 cc / (m ² · day · atm) or less at 25 ° C. The ink layer satisfies all the conditions (1) to (5) below, and the adhesive layer satisfies all the conditions (11) to (15) below; (1) the ink layer contains a polyamine Dried or hardened ink composition of polyurethane polyurea resin, vinyl chloride-vinyl acetate copolymer, pigment and organic solvent; (2) the polyurethane polyurea resin and the The total vinyl chloride-vinyl acetate copolymer contains 5% to 40% by mass of the vinyl chloride-vinyl acetate copolymer in 100% by mass; (3) the polyurethane polyurea resin contains A structural unit derived from a polymer polyol having a number average molecular weight of 400 to 5000, a polyurethane block derived from a structural unit derived from a polyisocyanate compound, and a chain extension unit derived from a compound having an amine group. The polyurethane block and the chain extension unit are separated by urea Whereas, 100% by mass of the polymer polyol having a number-average molecular weight of 400 to 5000 includes more than 5% by mass of polyester polyol; (4) mass of the polyurethane polyurea resin The average molecular weight is 15,000 to 70,000; (5) The total concentration of the urethane bond and urea bond contained in 1 g of the polyurethane polyurea resin is 1.3 mmol / g to 2.4 mmol / g; (11) The adhesive layer is a cured product of an adhesive composition containing a polyisocyanate component (A) and a polyol component (B); (12) The polyisocyanate component (A) includes an amine group having an isocyanate group The formate prepolymer (a) and 4,4'-diphenylmethane diisocyanate, further including at least one selected from the group consisting of 2,4'-diphenylmethane diisocyanate and toluene diisocyanate Isocyanate; (13) the urethane prepolymer having the isocyanate group (a) is a reaction product of an isocyanate component and a polyol requiring a polyether polyol, wherein the isocyanate component requires 4,4'-di Phenylmethane diisocyanate and further comprising a group selected from 2,4'-di At least one of the group consisting of phenylmethane diisocyanate and toluene diisocyanate, or a mixture of a reaction product of 4,4'-diphenylmethane diisocyanate and a polyol, and a mixture of a reaction product of an isocyanate component and a polyol And at least one of the polyols requires a polyether polyol, wherein the isocyanate component is at least one selected from the group consisting of 2,4'-diphenylmethane diisocyanate and toluene diisocyanate; (14) The polyol component (B) needs to contain a polyester polyol having a number average molecular weight of 500 or more and 3000 or less; (15) 4,4'-diphenylmethane contained in 100% by mass of the adhesive composition The total amount of diisocyanate, 2,4'-diphenylmethane diisocyanate, and toluene diisocyanate is 10% to 34% by mass. The laminated body according to item 1 of the scope of patent application, wherein the pigment contained in the ink layer is titanium oxide. The laminated body according to item 1 or item 2 of the scope of patent application, wherein the second substrate is formed by laminating a transparent film and a metal vapor deposition layer on one main surface of the transparent film, and the metal The vapor deposition layer is in contact with the adhesive layer. A method for manufacturing a laminated body, wherein the laminated body is sequentially laminated: a first substrate having visible light permeability, the ink layer, the adhesive layer, and an oxygen transmission rate at 100 ° C. of 100 cc / (m ² · Day · atm) The following second substrate, and includes the following steps (I) to (VI); (I-1) Preparation of a polyurethane polyurea resin having a number average molecular weight of 15,000 to 70,000 In the step, the polyurethane polyurea resin is a reaction product of a polymer polyol having a number average molecular weight of 400 to 5,000, a polyisocyanate compound and a compound having an amine group, and the number average molecular weight of 400 to 5,000. 100% by mass of the polymer polyol contains 5% by mass or more of the polyester polyol, and the total concentration of the urethane bond and the urea bond contained in 1 g of the polyurethane polyurea resin is 1.3 mmol / g to 2.4 mmol / g; (I-2) a step of preparing an ink composition containing the polyurethane polyurea resin, a vinyl chloride-vinyl acetate copolymer, a pigment, and Organic solvent, the polyurethane polyurea resin and the ethyl chloride -The total vinyl acetate copolymer contains 5 to 40 mass% of the vinyl chloride-vinyl acetate copolymer in 100 mass%; (II-1) a step of preparing a polyisocyanate component (A), the polymer The isocyanate component (A) contains an urethane prepolymer (a) having an isocyanate group and 4,4'-diphenylmethane diisocyanate, and further contains a material selected from the group consisting of 2,4'-diphenylmethane diisocyanate and At least one isocyanate component in the group consisting of toluene diisocyanate, and the urethane prepolymer (a) is a condition in which an isocyanate component and a polyol requiring a polyether polyol have an excess of isocyanate groups A reaction wherein the isocyanate component requires 4,4'-diphenylmethane diisocyanate and further includes at least one selected from the group consisting of 2,4'-diphenylmethane diisocyanate and toluene diisocyanate, Or obtained by separately reacting the isocyanate component with a polyol requiring a polyether polyol under the conditions of excess isocyanate groups, and then mixing them, wherein the isocyanate component requires 4,4'-diphenyl Alkane diisocyanate and at least one selected from the group consisting of 2,4'-diphenylmethane diisocyanate and toluene diisocyanate; (II-2) a step of preparing an adhesive composition, the adhesive composition The polyisocyanate component (A) is mixed with a polyol component (B) that needs to contain a polyester polyol having a number average molecular weight of 500 to 3000, and the polyisocyanate component (A) and the polyol component (B ) The total amount of 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate and toluene diisocyanate contained in a total of 100% by mass is 10% to 34% by mass; ( III) a step of applying the ink composition on the first substrate, and drying or curing to obtain the ink layer; (IV) applying the adhesive composition on the ink layer to form the ink composition A step of adhering the precursor of the adhesive layer; (V) a step of superposing the second substrate on the precursor of the adhesive layer; (VI) after step (V), advancing the precursor of the adhesive layer A step of hardening a material to form the adhesive layer. A method for manufacturing a laminated body, wherein the laminated body is laminated in this order: a first substrate having visible light transmittance, an ink layer, an adhesive layer, and an oxygen permeability at 25 ° C. of 100 cc / (m ² · day · atm ) The following second substrate, which includes the following steps (I) to (III), (VII) to (IX); (I-1) preparing a polyurethane having a number average molecular weight of 15,000 to 70,000 A step of an ester polyurea resin, the polyurethane polyurea resin is a reaction product of a polymer polyol having a number average molecular weight of 400 to 5000, a polyisocyanate compound and a compound having an amine group, and the number average 100% by mass of the polymer polyol having a molecular weight of 400 to 5000 includes 5% or more of a polyester polyol, and a urethane bond and urea contained in 1 g of a polyurethane polyurea resin The total concentration of bonds is 1.3 mmol / g to 2.4 mmol / g; (I-2) a step of preparing an ink composition containing the polyurethane polyurea resin, vinyl chloride-vinyl acetate Ester copolymers, pigments and organic solvents, the polyurethane polymers The total 100% by mass of the resin and the vinyl chloride-vinyl acetate copolymer contains 5 to 40% by mass of the vinyl chloride-vinyl acetate copolymer; (II-1) preparing a polyisocyanate component (A) Step, the polyisocyanate component (A) comprises an urethane prepolymer (a) having an isocyanate group and 4,4'-diphenylmethane diisocyanate, further comprising a component selected from 2,4'-di At least one isocyanate component in the group consisting of phenylmethane diisocyanate and toluene diisocyanate, and the urethane prepolymer (a) is an isocyanate component and a polyol requiring a polyether polyol The reaction is performed under an excess of isocyanate groups, wherein the isocyanate component requires 4,4'-diphenylmethane diisocyanate and further includes a group selected from the group consisting of 2,4'-diphenylmethane diisocyanate and toluene diisocyanate At least one of the groups, or obtained by separately reacting an isocyanate component with a polyol that requires a polyether polyol under the conditions of excess isocyanate groups and then mixing them, wherein the isocyanate is formed 4,4'-diphenylmethane diisocyanate is required, and at least one selected from the group consisting of 2,4'-diphenylmethane diisocyanate and toluene diisocyanate; (II-2) Preparation of adhesive The polyisocyanate component (A) is mixed with a polyol component (B) that needs to contain a polyester polyol having a number average molecular weight of 500 to 3000, and the polyisocyanate component ( A) Total amount of 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, and toluene diisocyanate contained in a total of 100% by mass with the polyol component (B) 10% by mass to 34% by mass; (III) a step of applying the ink composition on the first substrate and drying or curing to obtain the ink layer; (VII) the second substrate A step of applying the adhesive composition to form a precursor of the adhesive layer; (VIII) a step of superposing the ink layer on a precursor of the adhesive layer; (IX) in step (VIII) Then, the precursor of the adhesive layer is hardened to produce The steps of the adhesive layer are described.