JP2018027658A - Laminate and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate capable of forming a printed part excellent in appearance by coating an adhesive composition at a high speed, for example, a coating speed of 200 m/min and performing aging for a short time at a low temperature of 30°C or less when a base material excellent in gas barrier is used.SOLUTION: A laminate includes a transparent base material 1, a specific ink layer, a specific adhesives layer and a base material 2 having gas barrier in this order. The ink layer is the dry matter or the cured product of an ink composition including a specific polyurethane polyurea resin and a specific amount of vinyl chloride-vinyl acetate copolymer, and the adhesives layer is the cured product of an adhesive composition including a polyisocyanate component (A) and a polyol component (B). The polyisocyanate component (A) includes an urethane prepolymer (a) having an isocyanate group and 4,4'-diphenylmethane diisocyanate.SELECTED DRAWING: None

Description

  The present invention relates to a laminate having an ink layer and an adhesive layer, and more particularly to a laminate useful as a packaging material for foods, medical products, cosmetics and the like.

  The pasting of various plastic films and the pasting of a plastic film with a metal vapor-deposited film or a metal foil have been conventionally performed by a dry laminating method using a hydroxyl group / isocyanate solvent-based adhesive composition. However, since the dry laminating method uses an adhesive composition containing an organic solvent, special equipment for suppressing and preventing environmental pollution and fire is necessary.

In recent years, due to the demand for simple equipment, there has been a strong demand for removal of the adhesive composition from organic solvents, and research into solvent-free has been actively conducted.
For example, Patent Document 1 discloses a solventless laminating adhesive composition containing a polyol component (1) and a polyisocyanate component (2) composed of two types of polyisocyanate compounds.
Further, Patent Document 2 contains a polyol component (1) and a polyisocyanate component (2) essential for a trifunctional polyisocyanate compound, the branching point concentration is in a specific range, and the hydroxyl group mole number: isocyanate group. A solventless laminate adhesive composition having a mole number of 1: 1 to 1: 3 is disclosed.
Patent Document 3 discloses a solvent-free adhesive composition containing a polyol component (A) and an isocyanate component (B) essentially containing 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.
Patent Document 5 includes a polyisocyanate component (A) and a polyol component (B), and the polyisocyanate component (A) contains 2,4′-diphenylmethane diisocyanate (a1) and 4,4′-diphenylmethane diisocyanate ( It is a reactive product obtained by reacting a2) with a polyol essentially comprising a polyether polyol (a3) under conditions of excess isocyanate groups, and the polyol component (B) has a number average molecular weight of 500 or more and 3000 or less. An adhesive composition containing the polyester diol (b1) is essential and further contains at least one of a diol (b2) or a triol (b3) having a number average molecular weight of 50 or more and less than 500.
Further, claim 2 of Patent Document 6 includes a polyethylene terephthalate film layer (F1) for exterior packaging, a dry coating layer (P) for printing ink, a dry coating layer (C) for coating resin, and a solventless adhesive layer (A ), A plastic film laminate having a metal vapor-deposited layer or metal foil (M) and an interior plastic film layer (F2) in this order.
Patent Document 7 discloses a two-component curable 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 discloses an adhesive containing a specific polyisocyanate component (A) containing a urethane prepolymer made from polyether polyol and crude MDI, and a specific polyol component (B) containing polyester diol as an essential component. An agent composition is described.

JP-A-8-60131 JP 2003-96428 A JP 2006-57089 A JP 2011-162579 A JP 2014-159548 A JP 2010-280122 A JP 2002-249745 A Patent No. 5812219

  A laminate as a packaging material has a printing ink layer, an adhesive layer, and a substrate on one surface (hereinafter also referred to as a back surface and a back side) of a transparent substrate. The printing ink layer is seen from the opposite side (hereinafter also referred to as the surface or the front side) of the transparent substrate. The printing ink layer may be provided so as to cover the entire surface, or may be provided partially. The printing ink layer may be a single layer or a plurality of layers may be stacked. The portion where the printing ink layer is provided is also called an ink portion, and the portion where the printing ink layer is not provided is also called a plain portion.

  Solvent-free adhesive composition has no drying process and no solvent discharge, energy saving and good running cost, laminate after bonding plastic films together, plastic film and metal foil, metal deposition There are many merits such as no concern that the solvent remains in the laminate after the layers are bonded together. However, when a laminate as a packaging material is formed using a solventless adhesive composition and a substrate having a high gas barrier property (hereinafter also referred to as a barrier substrate) provided with a metal vapor deposition layer on a film. There was a problem that the skin-like appearance defect was liable to occur on the ink part.

  Patent Documents 1 to 4 describe that as the polyisocyanate component, a relatively mild reaction, specifically, an alicyclic polyisocyanate component or an aliphatic polyisocyanate component is used. However, the polyisocyanate component having a relatively mild reaction has a problem that the aging process requires 2 to 5 days at 40 to 50 ° C. Further, Patent Documents 1 to 4 do not describe improvement of appearance defects in the ink portion. In addition, an aging process means the "process which advances hardening of an adhesive bond layer."

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

  In [0013] and [0014] of Patent Document 6, a dry coating layer (P) of printing ink is provided between an outer 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 disclosed to improve the appearance of the ink part using a binder for printing ink. However, the processing speed specifically shown in the examples, that is, the adhesive coating speed is as low as 10 m / min. Since the solvent-free adhesive composition is solvent-free, until now, when the coating speed is increased, the coating surface becomes rough, and thus it has been impossible to achieve both improvement in coating speed and improvement in appearance. From the viewpoint of improving productivity, it is desirable that a solvent-free adhesive composition be a laminate having a good appearance of the ink part at the same level as the solvent-type adhesive composition, for example, at a coating speed of about 200 m / min. It has come to be.

  On the other hand, Patent Document 7 discloses that by using a solventless adhesive composition containing a specific amount of crystalline polyester, the appearance of the ink part is to be improved even at a coating speed of 200 m / min. ing. However, since crystalline polyester is used, poor appearance cannot be improved by low temperature aging at 40 ° C. or lower.

  Patent Document 8 describes that a laminate having excellent appearance can be obtained by coating at a speed of 200 m / min or more and aging at a low temperature for a short time. It was rare.

An object of the present invention is to use a substrate having excellent gas barrier properties, for example, a substrate having an oxygen permeability of 100 CC (m ² , 24 hr, 1 atm, 25 ° C.) or less at a high speed, for example, a coating speed of 200 m / min. An adhesive composition is applied, and a laminate having a good appearance of a printed portion is provided by aging at a low temperature of 30 ° C. or lower and in a short time.

This invention is made in view of the said subject, Comprising: This invention is below 100CC (m < ² >, 24hr, 1atm, at25 degreeC) with the transparent base material 1, a specific ink layer, a specific adhesive bond layer, and below. It is related with the laminated body which has the base material 2 of this in this order.
That is, the ink layer constituting the laminate of the present invention satisfies all the following conditions (1) to (5), and the adhesive layer satisfies all the following conditions (11) to (15).
(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 an amount of 5 to 40% by mass in a total of 100% by mass of the polyurethane polyurea resin and the vinyl chloride-vinyl acetate copolymer.
(3) The polyurethane polyurea resin comprises a structural unit derived from a polymer polyol having a number average molecular weight of 400 to 5000, a polyurethane block having a structural unit derived from a polyisocyanate compound, and a chain extension unit derived from a compound having an amino group. The polyurethane block and the chain extension unit are bonded by a urea bond, and contain 5% by mass or more of polyester polyol in 100% by mass of the polymer polyol having the number average molecular weight of 400 to 5000.
(4) The mass average molecular weight of the polyurethane polyurea resin is 15000-70000.
(5) The total concentration of urethane bonds and urea bonds contained in 1 g of the polyurethane polyurea resin is 1.3 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) contains a urethane prepolymer (a) having an isocyanate group and 4,4′-diphenylmethane diisocyanate.
(13) The polyisocyanate component (A) is a trimer of a bifunctional isocyanate monomer, a burette in which water is added to the bifunctional isocyanate monomer, and an adduct in which a monoalcohol is added to the bifunctional isocyanate monomer. It further contains a modified product of at least one bifunctional isocyanate monomer selected from the group consisting of:
(14) The polyisocyanate component (A) may further contain at least one isocyanate component selected from the group consisting of 2,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and xylene diisocyanate. .
(15) The urethane prepolymer (a) having an isocyanate group is a reaction product of 4,4′-diphenylmethane diisocyanate and a polyol essentially comprising a polyether polyol.
(16) In 100% by mass of the polyol component (B), 70 to 100% by mass of a polyether polyurethane polyol having a number average molecular weight of 200 or more and 3000 or less is included.
(17) The total amount of 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and xylene diisocyanate contained in 100% by mass of the adhesive composition is 10 to 34 masses. %.

  In the laminate of the present invention, the pigment contained in the ink layer is preferably titanium oxide.

  Moreover, it is preferable that the base material 2 which comprises the laminated body of this invention has a metal vapor deposition layer on one surface, and the said metal vapor deposition layer contacts an adhesive bond layer.

Furthermore, the present invention provides a laminate having a transparent substrate 1, a specific ink layer, a specific adhesive layer, and a substrate 2 having an oxygen permeability of 100 CC (m ² , 24 hr, 1 atm, 25 ° C.) or less in this order. It is a manufacturing method of this, Comprising: It is related with the manufacturing method of the laminated body containing following process (I)-(VI).
(I-1) 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 amino group, and the polymer polyol having a number average molecular weight of 400 to 5000 is 100% by mass. Polyurethane polyurea resin containing 5 mass% or more of middle polyester polyol, the total concentration of urethane bonds and urea bonds contained in 1 g of polyurethane polyurea resin is 1.3 to 2.4 mmol / g, and the number average molecular weight is 15000 to 70000 The process of preparing.
(I-2) The polyurethane polyurea resin, vinyl chloride-vinyl acetate copolymer, pigment, and organic solvent are contained, and the total amount of the polyurethane polyurea resin and the vinyl chloride-vinyl acetate copolymer is 100% by mass. And a step of preparing an ink composition containing 5 to 40% by mass of the vinyl chloride-vinyl acetate copolymer.

(II-1) After reacting 4,4′-diphenylmethane diisocyanate with a polyol essentially containing a polyether polyol under an isocyanate group-excess condition,
At least one bifunctional selected from the group consisting of a trimer of a bifunctional isocyanate monomer, a burette in which water is added to the bifunctional isocyanate monomer, and an adduct in which a monoalcohol is added to the bifunctional isocyanate monomer. A modified isocyanate monomer;
If necessary, mixing at least one isocyanate component selected from the group consisting of 2,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and xylene diisocyanate,
A urethane prepolymer (a) having an isocyanate group;
4,4′-diphenylmethane diisocyanate;
At least one bifunctional selected from the group consisting of a trimer of a bifunctional isocyanate monomer, a burette in which water is added to the bifunctional isocyanate monomer, and an adduct in which a monoalcohol is added to the bifunctional isocyanate monomer. A modified product of an isocyanate monomer,
Preparing a polyisocyanate component (A), which may further contain at least one isocyanate component selected from the group consisting of 2,4′-diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and xylene diisocyanate;
(II-2) A polyol component (B) containing 70 to 100% by mass of a polyether polyurethane polyol having a number average molecular weight of 200 or more and 3000 or less in the polyisocyanate component (A) and 100% by mass of the polyol component (B). Mix and
4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and xylene contained in a total of 100% by mass of the polyisocyanate component (A) and the polyol component (B) The process of preparing the adhesive composition whose total amount of diisocyanate is 10-34 mass%.
(III) A step of applying the ink composition to the transparent substrate 1 and drying or curing to obtain an 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 stacking the base material 2 on the precursor of the adhesive layer.
(VI) A step of curing the precursor of the adhesive layer to form an adhesive layer.

Furthermore, the present invention provides a laminate having a transparent substrate 1, a specific ink layer, a specific adhesive layer, and a substrate 2 having an oxygen permeability of 100 CC (m ² , 24h, 1 atm, 25 ° C.) or less in this order. It relates to another manufacturing method. That is, it is related with the manufacturing method of the laminated body containing following process (I)-(III), (VII)-(IX).
(I-1) 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 amino group, and the polymer polyol having a number average molecular weight of 400 to 5000 is 100% by mass. Polyurethane polyurea resin containing 5 mass% or more of middle polyester polyol, the total concentration of urethane bonds and urea bonds contained in 1 g of polyurethane polyurea resin is 1.3 to 2.4 mmol / g, and the number average molecular weight is 15000 to 70000 The process of preparing.
(I-2) The polyurethane polyurea resin, vinyl chloride-vinyl acetate copolymer, pigment, and organic solvent are contained, and the total amount of the polyurethane polyurea resin and the vinyl chloride-vinyl acetate copolymer is 100% by mass. And a step of preparing an ink composition containing 5 to 40% by mass of the vinyl chloride-vinyl acetate copolymer.

(II-1) After reacting 4,4′-diphenylmethane diisocyanate with a polyol essentially containing a polyether polyol under an isocyanate group-excess condition,
At least one bifunctional selected from the group consisting of a trimer of a bifunctional isocyanate monomer, a burette in which water is added to the bifunctional isocyanate monomer, and an adduct in which a monoalcohol is added to the bifunctional isocyanate monomer. A modified isocyanate monomer;
If necessary, mixing at least one isocyanate component selected from the group consisting of 2,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and xylene diisocyanate,
A urethane prepolymer (a) having an isocyanate group;
4,4′-diphenylmethane diisocyanate;
At least one bifunctional selected from the group consisting of a trimer of a bifunctional isocyanate monomer, a burette in which water is added to the bifunctional isocyanate monomer, and an adduct in which a monoalcohol is added to the bifunctional isocyanate monomer. A modified product of an isocyanate monomer,
Preparing a polyisocyanate component (A), which may further contain at least one isocyanate component selected from the group consisting of 2,4′-diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and xylene diisocyanate;
(II-2) A polyol component (B) containing 70 to 100% by mass of a polyether polyurethane polyol having a number average molecular weight of 200 or more and 3000 or less in the polyisocyanate component (A) and 100% by mass of the polyol component (B). Mix and
4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and xylene contained in a total of 100% by mass of the polyisocyanate component (A) and the polyol component (B) The process of preparing the adhesive composition whose total amount of diisocyanate is 10-34 mass%.
(III) A step of applying the ink composition to the transparent substrate 1 and drying or curing to obtain an ink layer.
(VII) A step of coating the adhesive composition on the substrate 2 to form a precursor of the adhesive layer.
(VIII) A step of overlaying the ink layer on the precursor of the adhesive layer.
(IX) A step of curing the adhesive layer precursor to form an adhesive layer.

According to the present invention, when a substrate having an oxygen permeability of 100 CC (m ² , 24 hr, 1 atm, 25 ° C.) or less and having excellent gas barrier properties is used, the adhesive composition is applied at a high speed, for example, at a coating speed of 200 m / min. Even when aging is performed at a low temperature of 30 ° C. or lower for a short time, an adhesive performance of 0.6 N or more can be obtained at a width of 15 mm, and a laminate having a good appearance of the printed portion can be provided.

The ink layer constituting the laminate of the present invention is formed from an 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 the present invention is a reaction product of a urethane prepolymer having an isocyanate group obtained by reacting a polymer polyol and a polyisocyanate compound and a compound having an amino group.

  The polymer polyol is a well-known polymer polyol for gravure inks and flexographic inks, and can be obtained by polymerization reaction, condensation reaction, natural product, etc., many of which have a number average molecular weight of 400 to 10,000. The polyurethane polyurea resin in the present invention contains a polymer polyol having a number average molecular weight of 400 to 5000 as an essential component. By including a polymer polyol having a number average molecular weight of 400 or more, the polyurethane polyurea resin has appropriate flexibility, so that it has excellent leveling properties when printing the ink composition on the transparent substrate 1, and the appearance of the resulting laminate is excellent. improves. By including a polymer polyol having a number average molecular weight of 5,000 or less, the cohesive strength of the resulting ink layer is increased and the penetration of the isocyanate monomer in the adhesive composition into the ink layer is suppressed. improves.

For the structure of the polymer polyol in the present invention, various known polymer polyols generally used in the production of polyurethane resins can be used, and one or more kinds may be used in combination. For example,
Polymer polyols or copolymers of polyether polyols (1) such as methylene oxide, ethylene oxide, propylene oxide, tetrahydrofuran;
Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2methyl-1,3-propanediol, 2ethyl-2butyl-1,3propanediol, 1,3-butanediol, 1,4-butane Diol, neopentyl glycol, pentanediol, 3-methyl-1,5-pentanediol, hexanediol, octanediol, 1,4-butynediol, 1,4-butylenediol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerin , Saturated or unsaturated low molecular weight polyhydric alcohols such as trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, sorbitol, pentaesitol, and adipic acid , Phthalic acid, isophthalic acid , Terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, speric acid, azelaic acid, sebacic acid, trimellitic acid, pyromellitic acid and other polycarboxylic acids such as these Polyester polyols (2) obtained by dehydration condensation or polymerization with anhydrides;
Polyester polyols (3) obtained by ring-opening polymerization of lactones such as cyclic ester compounds such as polycaprolactone, polyvalerolactone, poly (β-methyl-γ-valerolactone);
Polycarbonate polyols (4) obtained by reaction of the low-molecular polyhydric alcohols with, for example, dimethyl carbonate, diphenyl carbonate, ethylene carbonate, phosgene, etc .;
Polybutadiene glycols (5); glycols obtained by adding ethylene oxide or propylene oxide to bisphenol A (6);
It is obtained by copolymerizing one or more hydroxyethyl, hydroxypropyl acrylate, acrylhydroxybutyl, etc., or a corresponding methacrylic acid derivative thereof, for example, with acrylic acid, methacrylic acid or an ester thereof in one molecule. And acrylic polyol (7).

Among polymer polyols, polyester polyols are particularly excellent from the viewpoint of adhesion of the ink layer to the transparent substrate 1 and solubility in the solvent of the ink composition, and the polyurethane polyurea resin in the present invention has a number average. The polyester polyols are contained in an amount of 5% by mass or more in 100% by mass of the polymer polyol having a molecular weight of 400 to 5000. By containing 5% by mass or more of polyester polyols, it is possible to suppress penetration of the adhesive component into the resulting ink layer, and the laminate appearance and laminate strength are improved. The content of the polyester polyol is preferably 20 to 90% by mass, more preferably 40 to 80% by mass in 100% by mass of the polymer polyol.
Polyester polyols include diols having one or more branched structures selected from 2-methyl-1,3-propanediol, 2-ethyl-2butyl-1,3-propanediol, 3-methyl-1,5-pentanediol, and the like. Since the polyester polyol obtained by polymerizing adipic acid has a branched structure, it is particularly excellent in adhesion and solubility to the substrate. In particular, a polyester polyol obtained by polymerizing 3-methyl-1,5-pentanediol and adipic acid is preferable.

  Among the above-mentioned polymer polyols, in addition to the polyester polyols included as essential, a polymer polyol other than one or more polyester polyols can also be used in combination. Polyether polyols having high adhesion to 1 and excellent solubility in solvents are preferred. Polyether polyols are preferably propylene oxide polymers having moderate flexibility in terms of adhesion to the substrate.

  In addition to the polymer polyol, a low molecular polyol having a number average molecular weight of 400 or less can be optionally contained. As the structure of the low molecular polyol, various known low molecular polyols generally used in the production of polyurethane resins can be used, and one or two or more kinds may be used in combination. For example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2methyl-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-butylenediol, diethylene glycol, triethylene glycol, dipropylene glycol , Saturated or unsaturated low molecular polyols such as glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, sorbitol, pentaesitol, dimethylolbutane Acid, dimethylo Low molecular diols containing a carboxylic acid such as Rupuropion acid, low molecular triols such as trimethylol propane. Use of these low-molecular diols facilitates adjustment of the urethane bond density and introduction of functional groups into the polyurethane polyurea resin.

  Examples of the polyisocyanate compound used for forming the polyurethane polyurea resin include various known aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates that are generally used in the production of polyurethane resins. For example, 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3- Phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, cyclohexane-1 , 4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, Melyl diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate Bis-chloromethyl-diphenylmethane-diisocyanate, 2,6-diisocyanate-benzyl chloride, dimerisocyanate obtained by converting a carboxyl group of dimer acid into an isocyanate group, and the like. These diisocyanate compounds can be used alone or in admixture of two or more.

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

The compound having an amino group used in forming the polyurethane polyurea resin is composed of a chain extender for the purpose of extending the molecular weight of the urethane prepolymer and a terminal blocking agent for the purpose of stopping the reaction of the polyurethane polyurea resin. is there.

  Examples of the chain extender include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, and dicyclohexylmethane-4,4'-diamine. Furthermore, as a chain extender capable of adding a hydroxyl group to the side chain of the polyurethane polyurea resin, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di- Use amines having a hydroxyl group in the molecule such as 2-hydroxyethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypyrroleethylenediamine, di-2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, etc. I can do it. These chain extenders can be used singly or in combination of two or more. From the viewpoint of improving workability at the time of printing because the resulting ink composition exhibits excellent solubility in a solvent. It is preferable to use isophoronediamine and 2-hydroxyethylethylenediamine in combination.

  Examples of the terminal blocking agent include dialkyl monoamines such as di-n-butylamine, monoethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol, tri (hydroxymethyl) aminomethane, 2-amino Monoamines having a hydroxyl group such as 2-ethyl-1,3-propanediol can also be used. Furthermore, monoamine type amino acids such as glycine, alanine, glutamic acid, taurine, aspartic acid, aminobutyric acid, valine, aminocaproic acid, aminobenzoic acid, aminoisophthalic acid, sulfamic acid and the like can also be mentioned. By using monoamines having a hydroxyl group such as monoethanolamine, a hydroxyl group can be added to the end of the polyurethane polyurea resin.

  Furthermore, as the terminal blocking agent, a monovalent active hydrogen compound can be used in addition to the compound having an amino group described above. Examples of such compounds include alcohols such as ethanol and isopropyl alcohol.

  The polyurethane polyurea resin in the present invention is obtained by reacting a urethane prepolymer having an isocyanate group at a terminal with a compound having an amino group. That is, first, a polyol containing a polymer polyol and a polyisocyanate compound are reacted at a temperature of 10 to 100 ° C. using a solvent inert to an isocyanate group, if necessary, and further using a catalyst if necessary. A urethane prepolymer having an isocyanate group is produced. Next, the urethane prepolymer and the compound having an amino group are reacted at 10 to 80 ° C.

  The method for reacting the urethane prepolymer with the compound having an amino group is a method of gradually dropping the solution of the compound having an amino group into the urethane prepolymer solution, or the urethane prepolymer solution into the solution of the compound having an amino group. In the present invention, the reaction can be carried out by any method.

The polyurethane polyurea resin in the present invention has a mass average molecular weight of 15000 to 70000, preferably 30000 to 60000.
When the mass average molecular weight is 15000 or more, the pigment composition is excellent in dispersibility, so that the resulting ink composition is excellent in color development and the cohesive strength of the ink layer is also increased. Moreover, since it shows a high cohesive force, the penetration of the adhesive composition into the ink layer can be suppressed, so that the laminate appearance and the laminate strength are improved.
Since the weight average molecular weight is 70,000 or less, the resulting ink composition has excellent leveling properties when printed on the transparent substrate 1, and a smooth ink layer surface free from unevenness due to poor leveling can be obtained. In addition, voids and bubbles at the ink layer-adhesive layer interface are less likely to occur, and the appearance of the laminate is improved. Furthermore, the working efficiency in the printing process using the ink composition obtained is also improved.

  The urethane bond and urea bond in the present invention are a bond obtained by reacting a hydroxyl group and an isocyanate group, respectively, and a bond obtained by reacting an amino group and an isocyanate group, and the urethane bond and urea bond shown here. The total concentration of is the number of moles of each bond contained in 1 g of polyurethane polyurea resin.

  In the polyurethane polyurea resin in the present invention, the total concentration of urethane bonds and urea bonds is 1.3 to 2.4 mmol / g, preferably 1.4 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 on the obtained ink layer is difficult to permeate, and the appearance of the layered body is improved. By being 2.4 mmol / g or less, the solubility in a solvent is improved, the leveling property of the resulting ink composition is improved, and a more uniform ink layer can be formed, so the appearance of the laminate is improved. .

The concentration of urethane bonds depends on either the number average molecular weight of all polyols used in the reaction for obtaining the urethane prepolymer or the NCO / OH ratio, which is the molar ratio of hydroxyl groups to isocyanate groups in the reaction for obtaining the urethane prepolymer. It is possible to control.
The concentration of urea bonds is NCO / NH, which is the number average molecular weight of all the amino group compounds used, or the molar ratio of the isocyanate group of the urethane prepolymer to the primary or secondary amino group in the amino group compound. It can be controlled by the ratio. In the polyurethane polyurea resin in the present invention, the total concentration of urethane bonds and urea bonds is 1.3 to 2.4 mmol / g, and the concentration of each of urethane bonds and urea bonds is in the range of 0.5 to 1.2 mmol / g. It is preferable that it exists in.

  Next, the vinyl chloride-vinyl acetate copolymer (hereinafter sometimes referred to as vinyl acetate) contained in the ink composition of the present invention will be described. The ink composition in the present invention contains a vinyl chloride-vinyl acetate copolymer. The vinyl chloride-vinyl acetate copolymer has a vinyl chloride moiety and a vinyl acetate moiety as essential, and may have a vinyl alcohol-modified site or a maleic acid-modified site. The vinyl chloride-vinyl acetate copolymer preferably contains 85 to 95% by weight of vinyl chloride moiety and 1 to 15% by weight of vinyl acetate moiety in 100% by weight of the vinyl chloride-vinyl acetate copolymer. The molecular weight is preferably in the range of 20000 to 80000. Vinyl chloride-vinyl acetate copolymers are commercially available. For example, Solvein C, CL, CH, CN, CNL, C5R, A, AL, TA5R, TA3, TAO, M5, WACKER manufactured by Nissin Chemical Industry Co., Ltd. VINNOL E15 / 45, H14 / 36, H15 / 42, H40 / 43, H40 / 50, H20 / 45, E15 / 45M, H30 / 48M, H15 / 45M and the like manufactured by the company are listed.

Since the vinyl chloride-vinyl acetate copolymer is excellent in compatibility with the polyurethane polyurea resin and other components in the ink composition, it is suitable for producing a printed matter having a good appearance without pinholes. Furthermore, penetration of the adhesive composition component into the ink layer can be suppressed by the chemical resistance of the vinyl chloride moiety. Moreover, the adhesiveness of the ink layer to the transparent base material 1 becomes high due to the plasticity of the vinyl acetate portion, whereby a laminate having good laminate strength can be obtained.
It is important that the ink composition in the present invention contains 5 to 40% by mass of vinyl chloride-vinyl acetate copolymer in 100% by mass of the total solid content of polyurethane polyurea resin and vinyl chloride-vinyl acetate copolymer. It is preferable to contain 10-30 mass%. By being 5 mass% or more, it becomes difficult for the adhesive to penetrate into the ink layer, and the appearance of the laminate is improved. On the other hand, when the content is 40% by mass or less, the laminate strength of the laminate is improved.

  Among the vinyl chloride-vinyl acetate copolymers, for example, vinyl chloride-vinyl acetate copolymers containing hydroxyl groups, such as Solvein A, AL, TA5R, and TAO, are solvents other than toluene (hereinafter referred to as non-toluene). Also has excellent solubility in solvents other than ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone (hereinafter also referred to as non-ketones). When an ink composition is produced using a non-toluene non-ketone solvent and further printed, it is more preferable to contain the vinyl chloride-vinyl acetate copolymer containing the hydroxyl group.

  In the ink composition of the present invention, various resins other than the polyurethane polyurea resin and the vinyl chloride-vinyl acetate copolymer can be used in combination depending on the use and the substrate. Examples of resins used include polyurethane polyurea resins other than those described above, polyurethane resins, vinyl chloride-acrylic acid ester copolymers, chlorinated polypropylene resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, polyamide resins, Nitrocellulose resin, acrylic resin, polyester resin, alkyd resin, polyvinyl chloride resin, rosin resin, rosin modified maleic resin, terpene resin, phenol modified terpene resin, ketone resin, cyclized rubber, chlorinated rubber, butyral, petroleum resin And modified resins thereof. In particular, vinyl chloride-vinyl acetate copolymer is preferable. These resins can be used alone or in admixture of two or more, and the content thereof is preferably 0.5 to 20% by mass with respect to 100% by mass of the solid content of the ink composition.

  The ink composition in the present invention can use inorganic pigments and organic pigments as pigments. It is preferable that the pigment is contained in an amount sufficient to ensure the density of the printed matter, that is, 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 those used in general inks, paints and recording materials. Examples thereof include azo, phthalocyanine, anthraquinone, perylene, perinone, quinacridone, thioindigo, dioxazine, isoindolinone, quinophthalone, azomethine azo, dictopyrrolopyrrole, and isoindoline. Indigo ink is copper phthalocyanine, and transparent yellow ink is C.I. I. It is preferable to use PigmentNoYellow83.

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

  The ink layer generally consists of a multicolor ink layer and then a white ink layer that is laminated, but in white ink that is in direct contact with the adhesive layer, suppressing the penetration of the adhesive into the white ink layer is the appearance of the laminate. Most effective for improvement. Therefore, the pigment is a white inorganic pigment, and it is particularly preferable that the white inorganic pigment is titanium oxide. Titanium oxide is excellent in chemical resistance, so that it can suppress the penetration of the adhesive into the white ink layer, and is suitable for obtaining a laminate having a good appearance from the viewpoint of coloring power and hiding power. The titanium oxide is preferably surface-treated with an inorganic oxide, and examples thereof include silica treatment, alumina treatment, and silica / alumina treatment.

  The ink composition in the present invention may be used as a one-component ink composition, but for the purpose of further improving the heat and water resistance strength in accordance with the use of the laminate, a known isocyanate curing agent is added, It can also be used as a two-component ink composition. Examples of isocyanate curing agents include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and hexamethylene diisocyanate (HDI). Type polyisocyanate (isocyanurate) can be used, for example, adduct obtained from the reaction of 1 mol of trimethylolpropane and 3 mol of HDI, biuret obtained from the reaction of 1 mol of water and 3 mol of HDI, and cyclic HDI Examples include isocyanurate obtained from the trimerization reaction. When used as a two-component printing ink, the addition amount of the polyisocyanate curing agent is preferably 3 to 30% by mass with respect to 100% by mass of the solid content in the ink composition.

  Examples of the organic solvent used in the ink composition of the present invention include methyl acetate, ethyl acetate, normal propyl acetate, isopropyl acetate, isobutyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate and other ester solvents, methanol Known solvents such as alcohol solvents such as ethanol, normal propanol, isopropyl alcohol, normal butanol, propylene glycol monoethyl ether, propylene glycol monomethyl ether, and hydrocarbon solvents such as methylcyclohexane and ethylcyclohexane can be used. In recent years, there has been a demand to eliminate aromatic organic solvents such as toluene and xylene, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone from the viewpoint of the working environment. It is done.

  The ink composition in the present invention can be produced by dissolving and / or dispersing a resin, a pigment or the like in an organic solvent. Specifically, a pigment dispersion in which a pigment is dispersed in an organic solvent with a polyurethane polyurea resin, a vinyl chloride-vinyl acetate copolymer, and other resins, and other compounds as necessary is obtained. An ink composition can be produced by blending the polyurethane dispersion with a polyurethane polyurea resin, a vinyl chloride-vinyl acetate copolymer, and other resins, organic solvents, and other compounds as required. The process of obtaining the pigment dispersion is the kneading process, and the process of blending the pigment dispersion with polyurethane polyurea resin, vinyl chloride-vinyl acetate copolymer, other resins, organic solvents, and other compounds as necessary Also called a process.

  In order to stably disperse the pigment in the organic solvent, a dispersant may be used in combination in order to disperse the pigment further stably. As the dispersant, anionic, nonionic, cationic, amphoteric surfactants can be used. The dispersant is preferably contained in the ink composition in an amount of 0.01% by mass or more based on the total mass of the ink from the viewpoint of the storage stability of the ink and 5% by mass or less from the viewpoint of the suitability for lamination. Furthermore, it is more preferable that it is contained in the range of 0.05 to 2 mass%.

  The particle size distribution of the pigment in the pigment dispersion is adjusted by appropriately adjusting the size of the grinding media of the disperser, the filling rate of the grinding media, the dispersion treatment time, the discharge speed of the pigment dispersion, the viscosity of the pigment dispersion, and the like. be able to. As the disperser, generally used, for example, a roller mill, a ball mill, a pebble mill, an attritor, a sand mill and the like can be used.

  When air bubbles or unexpectedly coarse particles are included in the ink composition, it is preferably removed by filtration or the like in order to reduce the quality of the printed matter. A conventionally well-known filter can be used.

  The viscosity of the ink composition produced by the above method is 10 mPa · s or more from the viewpoint of preventing the pigment from settling and being appropriately dispersed, and 1000 mPa · s or less from the viewpoint of workability efficiency at the time of ink composition production or printing. A range is preferable. In addition, the said viscosity is a viscosity measured at 25 degreeC with the Tokimec B-type viscometer.

Next, the adhesive layer which comprises the laminated body of this invention is demonstrated. The adhesive layer is a cured product of an adhesive composition containing a polyisocyanate component (A) and a polyol component (B).
The polyisocyanate component (A) contained in the adhesive composition in the present invention will be described.
Hereinafter, 4,4′-diphenylmethane diisocyanate is converted to 4,4′-MDI,
2,4′-diphenylmethane diisocyanate to 2,4′-MDI,
Tolylene diisocyanate is TDI, xylylene diisocyanate is XDI,
Hexamethylene diisocyanate is HDI, isophorone diisocyanate is IPDI
Sometimes abbreviated.

The polyisocyanate component (A) contains a urethane prepolymer (a) having an isocyanate group and 4,4′-diphenylmethane diisocyanate.
Further, the polyisocyanate component (A) is composed of a trimer of a bifunctional isocyanate monomer, a burette body in which water is added to the bifunctional isocyanate monomer, and an adduct body in which a monoalcohol is added to the bifunctional isocyanate monomer. A modified product of at least one bifunctional isocyanate monomer selected from the group;
The polyisocyanate component (A) may contain at least one isocyanate component selected from the group consisting of 2,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and xylene diisocyanate.
The urethane prepolymer (a) can be obtained by reacting an isocyanate component and a polyol under an excess of isocyanate groups,
It is a reaction product of an isocyanate component essential for 4,4′-MDI and a polyol essential for polyether polyol. As the isocyanate component, 2,4′-MDI, TDI and the like can be used in addition to 4,4′-MDI.

That is, examples of the polyisocyanate component (A) used in the present invention include (A1) to (A3).
(A1) a urethane prepolymer (a) which is a reaction product of 4,4′-MDI and a polyol essentially comprising a polyether polyol;
4,4'-MDI,
A modified product of a bifunctional isocyanate monomer.
(A2) a urethane prepolymer (a) which is a reaction product of 4,4′-MDI and a polyol essentially comprising a polyether polyol;
4,4'-MDI,
A mixture of a modified product of a bifunctional isocyanate monomer and a bifunctional isocyanate monomer other than 4,4′-MDI.
(A3) urethane prepolymer (a) which is a reaction product of an isocyanate component essential for 4,4′-MDI and a polyol essential for polyether polyol;
4,4'-MDI,
A bifunctional isocyanate monomer other than 4,4′-MDI;
A modified product of a bifunctional isocyanate monomer.

The polyol for forming the urethane prepolymer (a) will be described.
The polyol contains a polyether polyol as an essential component, and can further contain a polyester polyol. Polyether polyols generally have a lower viscosity in the melted state than polyester polyols, so polyols for forming urethane prepolymers in the polyisocyanate component (A), which is a component of the solventless adhesive composition. It is important to make the polyether polyol essential. Furthermore, by using a polyester polyol in combination, the compatibility with the polyol component (B) described later can be enhanced, and the cohesive force of the adhesive layer can be enhanced.
When the polyester polyol is used in combination, it is preferably 50% by mass or less in terms of the viscosity of the adhesive composition in 100% by mass of the polyol.

  As the polyether polyol, for example, an oxirane compound such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran is polymerized using, for example, water, ethylene glycol, propylene glycol, trimethylolpropane, and glycerin as a low molecular weight polyol as an initiator. Examples include polyether polyols obtained.

As the polyether polyol, a bifunctional or trifunctional or higher functional polyol can be used. In addition, a plurality of different functional groups can be used in combination.
As the polyether polyol, those having a number average molecular weight of 100 or more and 5000 or less are preferable. A plurality of those having different molecular weights can be used in combination.

Examples of the polyester polyol include a polyester polyol obtained by reacting a polyvalent carboxylic acid component with a glycol component.
Examples of the polyvalent carboxylic acid component include polyvalent carboxylic acids such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, and sebacic acid, dialkyl esters thereof, or mixtures thereof. Examples of the glycol component include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3′-dimethylolheptane, poly And glycols such as oxyethylene glycol, polyoxypropylene glycol, and polytetramethylene ether glycol, or a mixture thereof.

  Examples of the low molecular diol include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3′-dimethylolheptane, Low molecular diols such as 2-methyl-1,3-propanediol or a mixture thereof can be mentioned.

As described above, the polyisocyanate component (A) in the present invention contains a urethane prepolymer (a) having an isocyanate group and 4,4′-MDI. The isocyanate monomer may be the remaining unreacted isocyanate monomer when the urethane prepolymer (a) is obtained, or may be added after obtaining the urethane prepolymer (a).
The polyisocyanate component (A) preferably has a number average molecular weight of 200 to 1,000, more preferably 500 to 900. Although the polyisocyanate component (A) includes the urethane prepolymer (a), it preferably has a molecular weight as described above by including 4,4′-MDI or the like.

As described above, the polyisocyanate component (A) in the present invention contains a modified product of a bifunctional isocyanate monomer.
The modified product of the bifunctional isocyanate monomer used in the present invention is a trimer of the bifunctional isocyanate monomer, a burette formed by adding water to the bifunctional isocyanate monomer, and a monoalcohol added to the bifunctional isocyanate monomer. Selected from the group consisting of adduct bodies.
As a bifunctional isocyanate monomer, for example,
Trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2 Aliphatic diisocyanates such as 1,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylcaproate,
1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methyl 2,4-cyclohexane diisocyanate, methyl 2 Cycloaliphatic diisocyanates such as 1,6-cyclohexane diisocyanate, 1,4-bis (isocyanate methyl) cyclohexane, 1,3-bis (isocyanate methyl) cyclohexane,
m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate or mixtures thereof, 4 Aromatic diisocyanates such as 4,4'-toluidine diisocyanate, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate,
1,3- or 1,4-xylylene diisocyanate or mixtures thereof, ω, ω′-diisocyanate-1,4-diethylbenzene, 1,3- or 1,4-bis (1-isocyanate-1-methylethyl) benzene Or an araliphatic diisocyanate such as a mixture thereof,
Organic triisocyanates such as triphenylmethane-4,4 ′, 4 ′ ″-triisocyanate, 1,3,5-triisocyanatebenzene, 2,4,6-triisocyanatotoluene, 4,4′-diphenyldimethylmethane And polyisocyanate monomers such as organic tetraisocyanates such as -2,2'-5,5'-tetraisocyanate.

  Examples of the monoalcohol for forming the adduct body include methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol, hexyl alcohol, Heptyl alcohol, octyl alcohol, capryl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, nonadecyl alcohol, eicosyl alcohol , Seryl alcohol, melyl alcohol and other aliphatic saturated alcohols; allyl alcohol Aliphatic unsaturated alcohols such as crotyl alcohol and propargyl alcohol, alicyclic alcohols such as cyclopentanol and cyclohexanol; aromatic alcohols such as benzyl alcohol and cinnamyl alcohol; heterocyclic alcohols such as furfuryl alcohol, etc. Is used.

Moreover, it is preferable that the polyisocyanate component (A) used for this invention contains 10 mass%-less than 21 mass% of isocyanate groups.
When the isocyanate group content of the polyisocyanate component (A) is within the above range, a laminate having a better appearance can be formed when a film base material having a high gas barrier property is used. The isocyanate group content (% by mass) is determined by titration with hydrochloric acid as described later.

Moreover, each ratio of 4,4'-MDI, 2,4'-MDI, TDI, XDI, IPDI contained in the polyisocyanate component (A) is 4,4'-MDI, 2,4'-MDI. , TDI, XDI, IPDI in total 100 mol%,
It is preferable that 4,4′-MDI is 25 mol% or more and 100 mol% or less.
When the composition ratio of 4,4′-MDI is in the above range, the coating appearance of the ink part in the laminate is improved and good adhesion performance can be exhibited without managing the aging temperature to 31 ° C. or higher. . When only 2,4′-MDI, TDI, XDI, and IPDI are used, sufficient adhesive performance cannot be exhibited by short-time aging.

Next, the polyol component (B) contained in the adhesive composition in the present invention will be described.
The polyol component (B) contains 70 to 100% by mass of a polyether polyurethane polyol having a number average molecular weight of 200 or more and 3000 or less in 100% by mass. The polyether polyurethane polyol is a reaction product obtained by reacting a polyether polyol and an isocyanate component such as 4,4′-MDI, 2,4′-MDI, or TDI under conditions of excess polyol.
By using the polyether polyurethane polyol as an essential component, the coating appearance of the ink part is improved and good adhesion performance can be exhibited. By using the polyol component (B) containing the polyether polyurethane polyol within the above range, it is possible to obtain a laminate having a good appearance when coating and laminating at high speed using a film base with high gas barrier properties. And good adhesive performance can be expressed.

The polyether polyol which is an essential raw material of the polyether polyurethane polyol will be described. Examples of the polyether polyol include polyether diol and polyether triol.
As the polyether diol, for example, an oxirane compound such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran and the like obtained by polymerizing, for example, water, ethylene glycol, propylene glycol and the like bifunctional low-part polyols as initiators. And ether diol.
Examples of the polyether triol include polyether triols obtained by polymerizing oxirane compounds such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran, for example, using low-part triols such as trimethylolpropane and glycerin as an initiator. .

The polyol component (B) can contain other polyol components such as a polyester polyol in addition to the polyether polyurethane polyol as long as the object of the present invention is not impaired.
Examples of the polyester polyol include polyvalent carboxylic acids such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, and sebacic acid, or dialkyl esters thereof, or mixtures thereof, and, for example, ethylene glycol, propylene glycol, diethylene glycol, butylene glycol. , Neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3′-dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, and other glycols Lactones such as polyester polyols or polycaprolactones, polyvalerolactones, poly (β-methyl-γ-valerolactones) obtained by reacting them with a mixture thereof Polyester polyols obtained by ring-opening polymerization.
Moreover, vegetable oils such as castor oil and polyester compounds derived from vegetable oils can also be used.

  Typical vegetable oils are: Asa seed oil, flaxseed oil, eno oil, psyllium oil, olive oil, cacao oil, kapok oil, kaya oil, mustard oil, kyounin oil, kiri oil, kukui oil, walnut oil, poppy oil, sesame oil , Safflower oil, radish seed oil, soybean oil, daikon oil, camellia oil, corn oil, rapeseed oil, niger oil, nuka oil, palm oil, castor oil, sunflower oil, grape seed oil, gentian oil, pine seed oil Cottonseed oil, palm oil, peanut oil, dehydrated castor oil, and the like.

A product obtained by further reacting an acid anhydride such as trimellitic anhydride with a part of the hydroxyl group in the polyol component (B) such as polyether polyurethane polyol or polyester diol can also be used.
By using the polyol component (B) to which the acid anhydride has been added, the adhesion can be improved when applied to a sheet-like substrate that is difficult to adhere. The amount of trimellitic anhydride to be added is preferably 0.1 to 5% by mass in 100% by mass of the polyol component (B).

The polyol component (B) can further contain a diol having a number average molecular weight of 50 or more and less than 500.
For example, polyester diol, polyether diol, polyether ester diol, polyester amide diol, acrylic diol, polycarbonate diol, ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl- Examples thereof include low molecular diols such as 1,5-pentanediol, 3,3′-dimethylolheptane, 2-methyl-1,3-propanediol, and mixtures thereof. Among these, low molecular diols are preferable from the viewpoint of reactivity.

  Examples of the polyether ester polyol include a polybasic acid obtained by reacting the above polyether diol with a dibasic acid such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, sebacic acid or the like or a mixture thereof. Examples include ether ester diols.

  The polyesteramide diol can be obtained, for example, by using an aliphatic diamine having an amino group such as ethylenediamine, propylenediamine, hexamethylenediamine as a raw material in the esterification reaction.

  Examples of acrylic diols include hydroxyethyl acrylate, hydroxypropyl acrylate, acrylic hydroxybutyl, etc., or their corresponding methacrylic acid derivatives containing one or more hydroxyl groups in one molecule, such as acrylic acid, methacrylic acid, etc. It is obtained by copolymerizing an acid or its ester.

  Examples of the polycarbonate diol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, and 1,9-nonane. One or more glycols selected from diol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol are dimethyl What was obtained by reaction with carbonate, diphenyl carbonate, ethylene carbonate, phosgene, etc. is mentioned.

  Moreover, as a low molecular weight triol, low molecular weight triols, such as castor oil, a trimethylol propane, glycerol, or mixtures thereof are mentioned. Among these, low molecular triols and polyether triols are preferable from the viewpoint of reactivity.

In the adhesive composition according to the present invention, when the number of hydroxyl groups in the polyol component (B) is 100 moles, the number of moles of isocyanate groups in the polyisocyanate component (A) is 120 to 400 moles. It is preferable.
When the number of hydroxyl groups in the polyol component (B) is 100 moles, the number of moles of isocyanate groups in the polyisocyanate component (A) is within the above range. Adhesive strength can be expressed.

The adhesive composition in the present invention contains 4,4′-MDI, 2,4′-MDI, TDI, HDI, contained in a total of 100 mass% of the polyisocyanate component (A) and the polyol component (B). The total amount of IPDI is 10 to 34% by mass, and preferably 12 to 30% by mass.
The total amount of 4,4′-MDI, 2,4′-MDI, TDI, HDI, and IPDI contained in the total 100 mass% of the polyisocyanate component (A) and the polyol component (B) is within the above range. As a result, a laminate having a better appearance can be obtained when a film base material having a high gas barrier property is used.

The adhesive composition in the present invention may further contain 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, a film substrate having a high gas barrier property can be used to obtain a laminate with a more external appearance when coating and laminating at high speed. If the particles are too small, the flow characteristics will not change much even if added, so the appearance will not change much.
Here, the average particle diameter is an average volume diameter and is a value obtained by a laser light scattering method.

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

  Examples of inorganic compound particles include aluminum oxide, aluminum silicate, aluminum hydroxide, alumina white, potassium sulfate, zinc oxide, zinc carbonate, magnesium metasilicate magnesium silicate, magnesium silicate, magnesium oxide, magnesium carbonate, and hydroxide. Magnesium, 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, rholite clay, silica Examples thereof include powders such as stone, mica, graphite, sericite, montmorillonite, sericite, sepiolite, bentonite, perlite, zeolite, wollastonite, fluorite, and dolomite. Among these, silica and talc are used for prizes.

  Examples of the organic compound particles include benzoguanamine resin, silicon resin, styrene resin, crosslinked polystyrene, epoxy resin, phenol resin, fluororesin, polyethylene resin, polyester resin, polyimide resin, polyamide resin, polyacetal resin, polyurethane resin, acetic acid. Examples thereof include powders of vinyl copolymer resins, polyphenylene oxide resins, nylon 6, nylon 12, cellulose, acrylic resins, methacrylic resins, and the like. Among these, benzoguanamine resin is used award.

The content of the particles is a particle having an average particle diameter of 1 × 10 ⁻⁴ mm or more to 4 × 10 ⁻⁴ mm or less with respect to 100 parts by mass in total of the polyisocyanate component (A) and the polyol component (B) ( C) is preferably contained in an amount of 0.01 to 10 parts by mass. By being in the said range, an external appearance and adhesive strength can be improved with sufficient balance.

  The particles can be mixed simultaneously with the polyisocyanate component (A) and the polyol component (B) component, or can be mixed in one of the components and the other can be mixed. The particles are preferably mixed in advance with the polyol component (B).

The adhesive composition in the present invention preferably does not contain a solvent, and the blending of each component is preferably performed at a temperature as low as possible within a range in which fluidity can be ensured, specifically at 25 ° C. or more and 80 ° C. or less. It is preferable to mix. The viscosity at 60 ° C. immediately after mixing the polyisocyanate component (A) and the polyol component (B) is preferably 50 mPa · s or more and 5000 mPa · s or less, more preferably 50 mPa · s or more and 3000 mPa · s or less. It is.
In the present invention, “immediately after mixing” means within 1 minute after uniform mixing, and the melt viscosity is a value determined by a B-type viscometer. If the melt viscosity at 60 ° C. exceeds 5,000 mPa · s, coating becomes difficult and it is difficult to ensure good workability, and if the coating temperature is 60 ° C. or lower, a good coating appearance may not be obtained. There is.
On the other hand, when the melt viscosity at 60 ° C. is less than 50 mPa · s, the initial cohesive force is weak, so that sufficient adhesive performance cannot be obtained, or the thickness of the coating film is uniform when the adhesive composition is applied to the substrate. It tends to cause poor appearance or warp.

The adhesive composition according to the present invention further requires additives such as antioxidants, ultraviolet absorbers, hydrolysis inhibitors, antifungal agents, thickeners, plasticizers, antifoaming agents, pigments and fillers. Can be used according to.
Moreover, in order to further improve the adhesive performance, an adhesion aid such as a silane coupling agent, phosphoric acid, phosphoric acid derivative, acid anhydride, or adhesive resin can be used. In addition, known catalysts, additives and the like can be used to control the curing reaction.

As the silane coupling agent, those having a functional group such as a vinyl group, an epoxy group, an amino group, an imino group, and a mercapto group and a functional group such as a methoxy group and an ethoxy group can be used.
For example, chlorosilane such as vinyltrichlorosilane, aminosilane such as N- (dimethoxymethylsilylpropyl) ethylenediamine, N- (triethoxysilylpropyl) ethylenediamine, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxy Examples thereof include epoxy silanes such as silane and vinyl silanes such as vinyl triethoxysilane.
The addition amount of the silane coupling agent is preferably 0.1 to 5% by mass with respect to the total adhesive composition.

  Among the oxygen oxyacids or derivatives thereof used in the present invention, the phosphorus oxyacid may be any one having at least one free oxygen acid, such as hypophosphorous acid, Examples thereof include phosphoric acids such as phosphorous acid, orthophosphoric acid and hypophosphoric acid, and condensed phosphoric acids such as metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid and ultraphosphoric acid. Examples of the phosphorus oxyacid derivative include those obtained by partially esterifying the phosphorus oxyacid with alcohols in a state in which at least one free oxyacid remains. Examples of these alcohols include aliphatic alcohols such as methanol, ethanol, ethylene glycol, and glycerin, and aromatic alcohols such as phenol, xylenol, hydroquinone, catechol, and phlorogricinol. One or two or more phosphorus oxyacids or derivatives thereof may be used. The amount of phosphorus oxygen acid or its derivative added is 0.01 to 10% by mass, preferably 0.05 to 5% by mass, more preferably 0.1 to 1% by mass, based on the total composition.

  The laminate of the present invention and the production method thereof will be described. The laminated body of this invention has the transparent base material 1, the white ink layer, the adhesive bond layer, and the base material 2 in this order as above-mentioned.

  Examples of the transparent substrate 1 include polyolefins such as polyethylene and polypropylene, polyethylene terephthalate (hereinafter also referred to as PET), polyesters such as polycarbonate and polylactic acid, polystyrene resins such as polystyrene, AS resin, and ABS resin, nylon, polyamide, poly There are films or sheets of vinyl chloride, polyvinylidene chloride, cellophane, paper, aluminum, etc., or composite materials of these, which are applied using the printing method described above and dried or cured by oven drying. A printed matter can be obtained by fixing. The base material may be subjected to a metal oxide or the like on its surface by a vapor deposition coating treatment and / or a coating treatment such as polyvinyl alcohol, and may further be subjected to a surface treatment such as a corona treatment.

The ink layer is a dried or cured product of the aforementioned ink composition containing a specific polyurethane polyurea resin and a specific amount of vinyl chloride-vinyl acetate copolymer.
The ink layer can be obtained by printing the ink composition on the transparent substrate 1 and drying or curing. The ink composition can be printed by a known printing method such as gravure printing or flexographic printing, but is particularly preferably printed by a gravure printing method. As the cylinder used for gravure printing, known ones such as engraving type and corrosion type are used.
The ink composition diluted with a diluent solvent to a viscosity and concentration suitable for gravure printing is supplied to each printing unit alone or mixed, passed through an oven after printing, dried or cured, and an ink layer is formed. It is formed. The oven temperature is usually 40 to 80 ° C., and the printing speed is usually 50 to 300 m / min. The ink layer is usually 0.5 to 5 g / m ² and preferably ¹ to 3.5 g / m ² .

As described above, the adhesive layer contains the specific polyisocyanate component (A) and the specific polyol component (B) in a total of 100% by mass of the polyisocyanate component (A) and the polyol component (B). 4,4′-MDI, 2,4′-MDI, TDI, HDI, IPDI is a cured product of the adhesive composition mixed so that the total amount is 10 to 34% by mass. Can be obtained by the method.
That is, the adhesive composition is applied on the white ink layer or the base material 2 having an oxygen permeability of 100 CC (m ² , 24 hr, 1 atm, 25 ° C.) or less, and the precursor of the adhesive layer is used. Form. The coating amount of the adhesive composition is appropriately selected according to the type of substrate 2 and the coating conditions, but is usually 1 to 5 g / m ² , preferably 1.5 to 4.5 g / m. ² .
Thereafter, the base material 2 having an oxygen permeability of 100 CC (m ² , 24 hr, 1 atm, 25 ° C.) or less is superimposed on the adhesive layer precursor, or the white ink layer, that is, the transparent base material 1 is applied to the adhesive layer precursor. After overlapping the surface of the white ink layer provided on the side where the transparent substrate 1 is not in contact, the precursor is cured by aging at room temperature or under heating, forming an adhesive layer, and laminating Manufacture the body. In the case of the adhesive composition in the present invention, the time required for aging is about 1 day. Moreover, in the case of the adhesive composition in this invention, sufficient adhesive performance can be expressed even if the environmental humidity in the case of coating-aging is high.

The base material 2 used has an oxygen permeability of 100 CC (m ² , 24 hr, 1 atm, 25 ° C.) or less. Oxygen permeability is affected by thickness. In the present application, an oxygen permeability of 100 CC or less can be used as the substrate 2 based on the oxygen permeability (hereinafter referred to as oxygen permeability coefficient) and thickness per unit thickness (1 μm).
For example, an ethylene-vinyl alcohol copolymer having an ethylene content of 56% has an oxygen permeability coefficient (m ² , 24 hr, 1 atm, 25 ° C.) of 3 CC and can be used even at 1 μm.
On the other hand, a plastic film having a large oxygen permeability coefficient as shown below can be used depending on the film thickness. That is, an acrylonitrile copolymer having an acrylonitrile content of 70% has an oxygen permeability coefficient of 300 CC and can be used if the film thickness is 3 μm or more.
Similarly,
The vinylidene chloride copolymer having an oxygen permeability coefficient of 400 CC can have a film thickness of 4 μm or more.
Nylon 6 having an oxygen permeability coefficient of 1700 CC has a film thickness of 17 μm or more.
Nylon 66 having an oxygen permeability coefficient of 1925CC can be set to a film thickness of 19.25 μm or more.
Polyethylene terephthalate having an oxygen transmission coefficient of 768CC has a film thickness of 7.68 μm or more.
If the terephthalic acid-bisphenol copolymer polyarylate having an oxygen permeability coefficient of 2580 CC is 25.8 μm or more in thickness,
If the polyacetal having an oxygen permeability coefficient of 4850 CC is less than 48.5 μm,
The polychlorotrifluoroethylene having an oxygen permeability coefficient of 650 CC has a film thickness of 6.5 μm or more.
Polyvinylidene fluoride having an oxygen transmission coefficient of 1300 CC can be formed to a thickness of 13 μm or more.
Each can be used as a substrate 2.

Moreover, the vapor deposition film which vapor-deposited aluminum, silicon oxide, aluminum oxide, etc. on the various plastic films can also be used as the base material 2. In many cases, the thickness of the vapor deposition layer is about 1 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 extremely small.
For example, an unstretched polypropylene film provided with an aluminum vapor deposition layer has an oxygen permeability of 20 to 10 CC (m ² , 24 hr, 1 atm, 25 ° C.),
A polyethylene terephthalate film provided with an aluminum vapor deposition layer has an oxygen permeability of ² to 0.3 CC (m ² , 24 hr, 1 atm, 25 ° C.),
A polyethylene terephthalate film provided with a vapor deposition layer of aluminum oxide has an oxygen permeability of 4 to 0.5 CC (m ² , 24 hr, 1 atm, 25 ° C.),
A polyethylene terephthalate film provided with a silicon oxide vapor-deposited layer has an oxygen permeability of 5 to 0.3 CC (m ² , 24 hr, 1 atm, 25 ° C.), and is used as the substrate 2 respectively.
Moreover, as metal foil, metal foils, such as stainless steel, iron, copper, lead, etc., have an oxygen permeability of 0 CC (m ² , 24 hr, 1 atm, 25 ° C.) regardless of the thickness.
The substrate 2 is preferably a plastic film provided with a vapor deposition layer on various plastic films or a metal foil, and particularly a metal vapor deposited on various plastic films (hereinafter sometimes referred to as vapor deposition film). The metal deposition layer is preferably in contact with the adhesive layer.

The oxygen permeability can be obtained according to the method of JISK7126 using an oxygen permeability measuring device. For example, Hitachi High-Technologies Corporation's MOCON oxygen permeability measuring device (OX-TRAN 2/21) generates a current proportional to the amount of oxygen that has passed through the sample as a carrier gas (
Nitrogen) is a device equipped with a coulometric sensor that measures the voltage change through a standard load resistance and converts it to oxygen permeability.

  Hereinafter, the present invention will be described more specifically with reference to examples. Unless otherwise indicated,% and part in Examples and Comparative Examples are based on mass.

<Method of measuring mass average molecular weight (Mw) and number average molecular weight (Mn)>
The mass average molecular weight (Mw) and the number average molecular weight (Mn) were measured using GPC (gel permeation chromatography) “ShodexGPCSystem-21” manufactured by Showa Denko KK. GPC is liquid chromatography that separates and quantifies substances dissolved in a solvent based on the difference in molecular size. Tetrohydrofuran is used as a solvent, and molecular weight is determined in terms of polystyrene.

<Method for measuring hydroxyl value>
About 1 g of a sample was accurately weighed in a stoppered Erlenmeyer flask and dissolved by adding 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution. Further, exactly 5 ml of an acetylating agent (a solution in which 25 g of acetic anhydride was dissolved in pyridine to make a volume of 100 ml) was added and stirred for about 1 hour. To this, phenolphthalein reagent is added as an indicator and lasts for 30 seconds. Thereafter, the solution was titrated with a 0.1N alcoholic potassium hydroxide solution until the solution turned light red.
The hydroxyl value was determined by the following (Formula 1). The hydroxyl value was a numerical value in the dry state of the resin (unit: mgKOH / g).
(Formula 1) Hydroxyl value (mgKOH / g) = [{(ba) × F × 28.25} / S] / (Nonvolatile content concentration / 100) + D
Where S: Amount of sample collected (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
b: Consumption of 0.1N alcoholic potassium hydroxide solution in the empty experiment (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution
D: Acid value (mgKOH / g)

<Method for measuring acid value>
About 1 g of a sample was accurately weighed in a stoppered Erlenmeyer flask and dissolved by adding 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution. To this was added a phenolphthalein test solution as an indicator, which was held for 30 seconds, and then titrated with a 0.1N alcoholic potassium hydroxide solution until the solution turned light red.
The acid value was determined by the following (Formula 2). The acid value is a numerical value of the dry state of the resin (unit: mgKOH / g)
(Formula 2) Acid value (mgKOH / g) = {(5.611 × a × F) / S} / (Nonvolatile content concentration / 100)
Where S: Amount of sample collected (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution

<Method for measuring NCO content (% by mass)>
About 1 g of a sample was refined into a 200 mL Erlenmeyer flask, and 10 mL of 0.5N di-n-butylamine (toluene solution) and 10 mL of toluene were added and dissolved therein. To this was added a phenolphthalein test solution as an indicator, which was kept for 30 seconds, and then titrated with a 0.25N hydrochloric acid solution until the solution became light red.
NCO (mass%) was calculated | required by the following (Formula 3).
(Formula 3) NCO (mass%) = {(ba) × 4.202 × F × 0.25} / S
Where S: Amount of sample collected (g)
a: Consumption of 0.25N hydrochloric acid solution (ml)
b: Consumption of ml of 0.25N hydrochloric acid solution for empty experiment (ml)
F: Potency of 0.25N hydrochloric acid solution

(Synthesis of polyurethane polyurea resin for ink composition)
[Synthesis Example 1-1]
To a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas introduction tube, polyester polyol A1 (a copolymer of Kuraray polyol P-2010, 3-methyl-1,5-pentanediol and adipic acid, several Average molecular weight 2000, manufactured by Kuraray Co., Ltd.) 11.17 parts, polyether polyol B1 (EXCENOL2020, propylene oxide polymer, number average molecular weight 2000, manufactured by Asahi Glass Co., Ltd.) 11.17 parts, isophorone diisocyanate (hereinafter also abbreviated as IPDI) 5.34 Parts, 4.36 parts of ethyl acetate and 0.003 part of tin 2-ethylhexanoate were reacted at 90 ° C. for 5 hours under a nitrogen stream, cooled by adding 7.5 parts of ethyl acetate, and an isocyanate group at the end. A solution of urethane prepolymer having was obtained.
Next, 1.97 parts of isophoronediamine (hereinafter also abbreviated as IPDA), 0.2 part of 2-hydroxyethylethylenediamine, 0.33 parts of di-n-butylamine, 30.13 parts of ethyl acetate and isopropyl alcohol (hereinafter also abbreviated as IPA) 28 The obtained urethane prepolymer solution was gradually added to the mixture of the parts at room temperature, and then reacted at 50 ° C. for 1 hour to give a polyurethane polyurea resin solution (PU1) having a solid content of 30% and a weight average molecular weight of 15,000. Got.
In addition, in this synthesis example, the solution of the urethane prepolymer obtained by amines is dripped, and chain extension reaction is performed.

[Synthesis Example 1-2]
A polyurethane polyurea resin solution (PU2) was obtained in the same manner as in Synthesis Example 1-1 with the charging ratio shown in Table 1.

[Synthesis Example 1-3]
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 11.21 parts of polyester polyol A1, 11.21 parts of polyether polyol B1, and 5.36 parts of IPDI, 4.36 parts of ethyl acetate and 0.003 part of tin 2-ethylhexanoate were charged, reacted at 90 ° C. for 5 hours under a nitrogen stream, cooled by adding 7.5 parts of ethyl acetate, and a urethane having an isocyanate group at the end. A prepolymer solution was obtained.
Next, 1.87 parts of IPDA, 0.2 part of 2-hydroxyethylethylenediamine, 0.17 part of di-n-butylamine, 30.13 parts of ethyl acetate and 28 parts of IPA were added to the obtained urethane prepolymer solution. The mixture was gradually added at room temperature and then reacted at 50 ° C. for 1 hour to obtain a polyurethane polyurea resin solution (PU3) having a solid content of 30% and a weight average molecular weight of 50000.
In this synthesis example, amines were dropped into the obtained urethane prepolymer solution to carry out a chain extension reaction.

[Synthesis Examples 1-4 to 1-8]
Polyurethane polyurea resin solutions (PU4 to PU8) were obtained in the same manner as in Synthesis Example 1-1 at the charging ratio shown in Table 1.
Polyester polyol A2 and polyether polyol B2 are as follows.
Polyester polyol A2: Kuraray polyol P-5010, a copolymer of 3-methyl-1,5-pentanediol and adipic acid, number average molecular weight 5000, manufactured by Kuraray Co., Ltd.
Polyether polyol B2: EXCENOL420, polymer of propylene oxide, number average molecular weight 400, manufactured by Asahi Glass.

[Synthesis Examples 1-9 to 1-13]
Polyurethane polyurea resin solutions (PUs 9 to 13) were obtained in the same manner as in Synthesis Example 1-1 with the charging ratios shown in Table 2.

(Adjustment of ink composition)
[Production Example 1]
5 parts of polyurethane polyurea resin solution (PU1), 5 parts of vinyl chloride-vinyl acetate copolymer solution C1 (Solvain TA5R, manufactured by Nissin Chemical Industry Co., Ltd., diluted with ethyl acetate, solid content 30% by mass), titanium oxide (TITONER 45M) , Manufactured by Sakai Chemical Co., Ltd.), mixed with 30 parts of ethyl acetate / IPA mixed solvent (mass ratio 75/25) and mixed with a sand mill, 32.5 parts of polyurethane polyurea resin solution (PU1), vinyl chloride-acetic acid After 7.5 parts of vinyl copolymer solution C1 and 10 parts of an ethyl acetate / IPA mixed solution (mass ratio 75/25) were mixed with stirring, a mixed solvent of methyl ethyl ketone, normal propyl acetate, and IPA (mass ratio 40:40:20). The ink composition (i-1) was obtained by diluting with Zahn cup # 3 (manufactured by Kogaisha) to 15 seconds.

[Production Examples 2 to 22]
Ink compositions (i-2 to i-22) were obtained in the same manner as in Production Example 1-1 with the charging ratios in Table 3 and Table 4. In addition to the titanium oxide as the pigment, C.I. I. Pigment Yellow 83 was used.
Furthermore, as resins other than the polyurethane polyurea resin solution and the vinyl chloride-vinyl acetate copolymer solution C1, the following resins were used as resin solutions diluted with ethyl acetate to a solid content of 30% by mass.
Vinyl chloride-vinyl acetate copolymer solution C2 (Solvine CL, manufactured by Nissin Chemical Industry Co., Ltd.)
Vinyl chloride-vinyl acetate copolymer solution C3 (Solvine AL, manufactured by Nissin Chemical Industry Co., Ltd.)
Nitrified cotton solution (DLX5-8, manufactured by Nobel Enterprises)

Synthesis of polyisocyanate component (α) for adhesive composition (Synthesis Example 101)
129 parts of polypropylene glycol (hereinafter referred to as PPG-400) having a number average molecular weight of about 400, 1018 parts of polypropylene glycol (hereinafter referred to as PPG-2000) having a number average molecular weight of about 2000, and about 400 having a number average molecular weight obtained by adding polypropylene glycol to glycerin. 85 parts of triol (hereinafter referred to as PPG-400-3 functional) and 670 parts of 4,4′-MDI were charged into a reaction vessel and heated at 70 ° C. to 80 ° C. for 3 hours with stirring under a nitrogen gas stream for urethanization. The reaction was performed to obtain a polyisocyanate composition α- (1) containing polyurethane polyisocyanate (a) and unreacted 4,4-diphenylmethane diisocyanate.
The composition α- (1) had an isocyanate group content of 6.9% and an MDI monomer content of 23%.

(Synthesis Example 102)
477 parts of adipic acid (hereinafter referred to as ADA) and 323 parts of propylene glycol were charged into a reaction vessel, and the mixture was heated to 150 ° C. to 240 ° C. with stirring under a nitrogen gas stream to carry out an esterification reaction. When the acid value reached 1.3 (mgKOH / g), the reaction temperature was set to 200 ° C., the pressure inside the reaction vessel was gradually reduced, and the reaction was allowed to proceed at 1.3 kPa or less for 30 minutes. ), A hydroxyl group value of 56.1 (mgKOH / g), and a number average molecular weight of about 2000, a polyester diol 1 having hydroxyl groups at both ends was obtained.
Obtained polyester diol 1 222 parts, PPG-400 112 parts, PPG-2000 666 parts, PPG-400-3 functional 72 parts, 4,4'-MDI 800 parts, charged in a reaction vessel, nitrogen A polyisocyanate composition α- () containing polyurethane polyisocyanate (a) and unreacted 4,4-diphenylmethane diisocyanate is obtained by heating at 70 ° C. to 80 ° C. for 3 hours with stirring under a gas stream to carry out urethanization reaction. 2) was obtained.
The composition α- (2) had an isocyanate group content of 10.3% and an MDI monomer content of 28%.

(Synthesis Examples 103-104)
According to the composition shown in Table 5, polyisocyanate α- (3) and polyisocyanate α- (4), which are polyether polyurethane polyisocyanate resins, were obtained in the same manner as in Synthesis Example 101 and Synthesis Example 102.

(Formulation example 201)
Polyisocyanate composition α- (1) obtained in Synthesis Example 101: 700 parts, 200 parts of an HDI burette, and 100 parts of 2,4MDI were mixed to obtain polyisocyanate component A- (1).

(Formulation examples 201-209)
According to the composition shown in Table 6, polyisocyanate components A- (2) to A- (9) were obtained in the same manner as in Formulation Example 301.

Synthesis of polyether polyurethane polyol component for adhesive composition (Synthesis Example 301)
400 parts of PPG-400, 200 parts of PPG-2000, 400 parts of PPG-400-3 functionality, and 4,4′-MDI: 150 parts were charged in a reaction vessel and stirred at 70 ° C. under a nitrogen gas stream. A urethanization reaction was carried out by heating at 80 ° C. for 3 hours to obtain a polyether polyurethane polyol having a number average molecular weight of 500 and a hydroxyl value of 220 (mgKOH / g). Hereinafter, this resin is referred to as polyether polyurethane polyol b1- (1).

(Synthesis Examples 302 and 303)
According to the composition shown in Table 7, polyether polyurethane polyol b1- (2) and polyether polyurethane polyol b1- (3) were obtained in the same manner as in Synthesis Example 301.

(Formulation example 403)
90 parts of the polyether polyurethane polyol b1- (1) obtained in Synthesis Example 301 and 10 parts of diethylene glycol were mixed to obtain a polyol component B- (3).

(Formulation example 404)
Adipic acid: 208 parts and diethylene glycol: 192 parts were charged into a reaction vessel, and heated to 150 ° C. to 240 ° C. with stirring under a nitrogen gas stream to conduct an esterification reaction. When the acid value reached 1.3 (mgKOH / g), the reaction temperature was set to 200 ° C., the pressure inside the reaction vessel was gradually reduced, and the reaction was performed at 1.3 kPa or less for 30 minutes. ), A hydroxyl group value of 56.1 (mgKOH / g) and a number average molecular weight of about 2000, a polyester diol 2 having hydroxyl groups at both ends was obtained.
70 parts of the polyether polyurethane polyol b1- (1) obtained in Synthesis Example 201 and 2:30 parts of the polyester diol were mixed to obtain a polyol component B- (4).

(Formulation example 407)
The polyether polyurethane polyol b1- (1) obtained in Synthesis Example 301: 60 parts and the polyester diol 2:40 parts were mixed to obtain a polyol component B- (7).

(Production Example 501)
100 parts of the polyisocyanate component A- (1) obtained in Formulation Example 201 and 50 parts of the polyol component B- (1) obtained in Formulation Example 401 are mixed at 60 ° C. to obtain a solventless adhesive composition AD1. Obtained.
In addition, the said solventless type adhesive composition AD1 contains 156 mol of isocyanate groups derived from polyisocyanate component A- (1) with respect to 100 mol of hydroxyl groups in the polyol component.
The amount of the isocyanate group with respect to 100 mol of the hydroxyl group is determined as follows.
Amount of isocyanate group per 100 mol of hydroxyl group = [isocyanate group (eq.) / Hydroxyl group (eq.)] × 100
Isocyanate group (eq.) = NCO content (mass%) / (42 × 100)
Hydroxyl group (eq.) = Hydroxyl value / 56100

Further, 4,4′-MDI, 2,4′-MDI, 2,2′-MDI, TDI, HDI, IPDI (hereinafter referred to as isocyanate monomer) contained in 100% of the solventless adhesive composition The total rate of was 17.3%.
Isocyanate monomer content is the sum of peak areas derived from MDI and IPDI monomers near Mn = 200 to 300 and peak areas derived from TDI and HDI monomers near Mn = 100 to 200, as observed on the GPC chart. The area is divided by the total area of all peaks observed on the GPC chart.
Isocyanate monomer content (%) = (total peak area of isocyanate monomer / total area of all peaks) × 100

(Production Examples 502 to 516)
Adhesive composition AD2-AD16 was obtained in the same manner as in Production Example 501 according to the composition shown in Table 9.

[Examples 1 to 13], [Comparative Examples 1 to 9]
[Production of printed matter]
The ink compositions i-1 to i-22 obtained in Production Examples 1 to 22 are corona-treated PET, which is a transparent substrate 1, at a printing speed of 50 m / min by a gravure printing machine equipped with a gravure plate having a plate depth of 30 μm. The film was printed on a film (Toyobo Ester Film E5100 # 12) and dried or cured by passing through an oven at 60 ° C. to form an ink layer on the PET film.

[Production of laminate]
Using a solventless test coater, the solventless adhesive composition AD2 obtained in Production Example 501 was applied to the surface of the ink layer printed on the OPP film at a temperature of 60 ° C. and a coating speed of 200 m / min. (Coating amount: 2 g / m ² ) An aluminum-deposited unstretched polypropylene film (hereinafter referred to as VMCPP, thickness: 25 μm) having an oxygen permeability of 20 CC (m ² , 24 h, 1 atm, 25 ° C.) on the coated surface. The vapor deposition surface of was laminated | stacked and the laminated body (pre laminated body) of the preparation stage was obtained.
These pre-laminated bodies were aged in an environment of 25 ° C. and 80% RH for 1 day to cure the adhesive layer, thereby preparing 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 according to the following method. The results are shown in Table 10.

(Adhesive strength)
The laminate was cut to a length of 300 mm and a width of 15 mm to obtain a test piece. Using an Instron type tensile tester, the sample was pulled at a peeling rate of 300 mm / min in an environment of 25 ° C., and the T-type peel strength (N) between PET / VMCP was measured at a width of 15 mm. This test was performed 5 times, the average value was calculated | required, and the following references | standards evaluated.
5: Adhesive force 1.5N or more 4: Adhesive force 1.0N or more, less than 1.5N 3: Adhesive force 0.6N or more, less than 1.0N 2: Adhesive force 0.3N or more and less than 0.6N 1: Adhesive force Less than 0.3N

(Layer interface state)
The vapor deposition part was visually observed through the ink layer and the adhesive layer from the transparent substrate 1 side, and evaluated according to the following criteria.
5: No yuzu skin-like pattern or small spot-like pattern is observed in the vapor deposition part.
4: A small spot-like pattern is not observed in the vapor deposition part, but a slightly skin-like pattern is observed. Level that is not problematic for use.
3: A small spot-like pattern is not observed in the vapor deposition part, but many yuzu skin-like patterns are observed. Level that is not problematic for use.
2: A small spot-like pattern as well as a yuzu-skin-like pattern is somewhat observed on the deposition surface.
1: Many small spot-like patterns are observed on the vapor deposition surface as well as the skin-like pattern.

  As shown in Table 10, it can be seen that Examples 1 to 14 in which an ink layer was formed with the ink composition of the present invention were excellent in appearance and adhesive strength after aging at 25 ° C. for 1 day. On the other hand, in Comparative Example 1, the molecular weight of the polyurethane polyurea resin is low, the cohesive force of the ink layer is insufficient, and the adhesive strength is particularly inferior. In Comparative Example 2, since the polyurethane polyurea resin has a high molecular weight and cannot form a uniform ink layer, the appearance of the laminate is inferior. 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 is low, the isocyanate monomer in the adhesive composition easily penetrates into the ink layer, and the adhesive strength is also the appearance of the laminate. However, the laminate appearance is particularly bad. In Comparative Example 4, the total concentration of urethane bonds and urea bonds in the polyurethane polyurea resin is low, and the isocyanate monomer in the adhesive composition easily penetrates into the ink layer, resulting in poor adhesive strength and laminate appearance. In Comparative Example 5, since the total concentration of urethane bonds and urea bonds of the polyurethane polyurea resin in the ink layer is higher than 2.4 mmol / g, a uniform ink layer cannot be formed, so that the laminate appearance is inferior. In addition, since the adhesion of the ink layer to the transparent substrate tends to decrease, the adhesive force is also low. In Comparative Examples 6 and 7, the ink composition did not contain any vinyl chloride-vinyl acetate copolymer, and in Comparative Example 8, the polyurethane polyurea resin and the vinyl chloride-vinyl acetate copolymer were 100% by mass in total. A vinyl chloride-vinyl acetate copolymer is contained in a proportion of 5% or less. In Comparative Examples 6 to 8, since the chemical resistance derived from the vinyl chloride-vinyl acetate copolymer in the ink layer was extremely inferior, the isocyanate monomer in the adhesive composition was added to the ink layer as in Comparative Examples 3 and 4. Penetration and inferior laminate appearance and adhesion. In Comparative Example 9, since the vinyl chloride-vinyl acetate copolymer is included beyond the scope of the present invention, the adhesion of the ink layer to the transparent substrate is reduced, and the adhesive strength is particularly inferior.

[Examples 14 to 22] [Comparative Examples 10 to 15]
As shown in Table 11, solvent-free adhesive composition AD1 obtained in Production Examples 501, 503 to 516 was used instead of adhesive composition AD2 using i-3 instead of ink composition i-1. , 3 to 16 were used, and a laminate was obtained in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 11.

As shown in Table 11, it turns out that Examples 14-22 which formed the adhesive bond layer with the adhesive composition in this invention are excellent in the external appearance and adhesive force after 25 degreeC 1 day aging.
On the other hand, Comparative Example 10 does not use 4,4′-MDI in the urethane prepolymer, and uses only 2,4-MDI, so the reaction rate is too slow and after aging at 25 ° C. for 1 day. The adhesive strength of is not enough.
In Comparative Example 11, since the polyether polyurethane polyol b1- (3) having a mass average molecular weight of 3200 was used as the polyol component B- (5) as the polyol component (B), the smoothness during coating was lowered and the appearance was poor. It becomes.
In Comparative Example 12, tripropylene glycol having a weight average molecular weight of 191 was used as polyol B- (6) as the polyol component (B), so that the reaction rate with the isocyanate component (A) was too fast and the adhesive was in the middle of curing. The appearance is not sufficient because the leveling properties of the layer are reduced.
Since the comparative example 13 uses 40% of polyester polyol as the polyol component (B), the compatibility between the polyol component (B) and the polyisocyanate component (A) is lowered, so that the appearance is lowered.
Since Comparative Example 14 contains 34.2% of the isocyanate monomer after blending, the appearance of the laminate after coating is not sufficient due to the penetration of the isocyanate component into the ink.
In Comparative Example 15, since 34.2% of the isocyanate monomer is contained in the adhesive after blending, the appearance of the laminate after coating is not sufficient due to the penetration of the isocyanate component into the ink.

[Examples 25 to 36] [Comparative Examples 16 to 24]
As shown in Table 12, a laminate is obtained by operating in the same manner as in Example 1 except that the solventless adhesive composition AD10 obtained in Production Example 410 is used instead of the adhesive composition AD1. , And evaluated in the same manner. The results are shown in Table 12.

  From Table 12, it can be confirmed that even when the adhesive composition is changed, the tendency is the same as in Table 10.

Claims (5)

A laminate having a transparent base material 1, an ink layer, an adhesive layer, and a base material 2 having an oxygen permeability of 100 CC (m ² , 24 hr, 1 atm, 25 ° C.) or less in this order,
The following (1) to (5) for the ink layer and the following (11) to (1) for the adhesive layer
A laminate that satisfies all the conditions of 6).
(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 an amount of 5 to 40% by mass in a total of 100% by mass of the polyurethane polyurea resin and the vinyl chloride-vinyl acetate copolymer.
(3) The polyurethane polyurea resin comprises a structural unit derived from a polymer polyol having a number average molecular weight of 400 to 5000, a polyurethane block having a structural unit derived from a polyisocyanate compound, and a chain extension unit derived from a compound having an amino group. The polyurethane block and the chain extension unit are bonded by a urea bond, and contain 5% by mass or more of polyester polyol in 100% by mass of the polymer polyol having the number average molecular weight of 400 to 5000.
(4) The mass average molecular weight of the polyurethane polyurea resin is 15000-70000.
(5) The total concentration of urethane bonds and urea bonds contained in 1 g of the polyurethane polyurea resin is 1.3 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) contains a urethane prepolymer (a) having an isocyanate group and 4,4′-diphenylmethane diisocyanate.
(13) The polyisocyanate component (A) is a trimer of a bifunctional isocyanate monomer, a burette in which water is added to the bifunctional isocyanate monomer, and an adduct in which a monoalcohol is added to the bifunctional isocyanate monomer. It further contains a modified product of at least one bifunctional isocyanate monomer selected from the group consisting of:
(14) The polyisocyanate component (A) may further contain at least one isocyanate component selected from the group consisting of 2,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and xylene diisocyanate. .
(15) The urethane prepolymer (a) having an isocyanate group is a reaction product of 4,4′-diphenylmethane diisocyanate and a polyol essentially comprising a polyether polyol.
(16) In 100% by mass of the polyol component (B), 70 to 100% by mass of a polyether polyurethane polyol having a number average molecular weight of 200 or more and 3000 or less is included.
(17) The total amount of 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and xylene diisocyanate contained in 100% by mass of the adhesive composition is 10 to 34 masses. %.   The laminate according to claim 1, wherein the pigment contained in the ink layer is titanium oxide.   The laminate according to claim 1 or 2, wherein the substrate 2 has a metal vapor deposition layer on one surface of the transparent film, and the metal vapor deposition layer is in contact with the adhesive layer. It is a manufacturing method of the laminated body which has the transparent base material 1, the ink layer, the adhesive bond layer, and the base material 2 with an oxygen permeability of 100 CC (m ² , 24 hr, 1 atm, 25 ° C.) or less in this order. The manufacturing method of the laminated body containing (I)-(VI).
(I-1) 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 amino group, and the polymer polyol having a number average molecular weight of 400 to 5000 is 100% by mass. Polyurethane polyurea resin containing 5 mass% or more of middle polyester polyol, the total concentration of urethane bonds and urea bonds contained in 1 g of polyurethane polyurea resin is 1.3 to 2.4 mmol / g, and the number average molecular weight is 15000 to 70000 The process of preparing.
(I-2) The polyurethane polyurea resin, vinyl chloride-vinyl acetate copolymer, pigment, and organic solvent are contained, and the total amount of the polyurethane polyurea resin and the vinyl chloride-vinyl acetate copolymer is 100% by mass. And a step of preparing an ink composition containing 5 to 40% by mass of the vinyl chloride-vinyl acetate copolymer.

(II-1) After reacting 4,4′-diphenylmethane diisocyanate with a polyol essentially containing a polyether polyol under an isocyanate group-excess condition,
At least one bifunctional selected from the group consisting of a trimer of a bifunctional isocyanate monomer, a burette in which water is added to the bifunctional isocyanate monomer, and an adduct in which a monoalcohol is added to the bifunctional isocyanate monomer. A modified isocyanate monomer;
If necessary, mix at least one isocyanate component selected from the group consisting of 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and xylene diisocyanate,
A urethane prepolymer (a) having an isocyanate group;
4,4′-diphenylmethane diisocyanate;
At least one bifunctional selected from the group consisting of a trimer of a bifunctional isocyanate monomer, a burette in which water is added to the bifunctional isocyanate monomer, and an adduct in which a monoalcohol is added to the bifunctional isocyanate monomer. A modified product of an isocyanate monomer,
Preparing a polyisocyanate component (A), which may further contain at least one isocyanate component selected from the group consisting of 2,4′-diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and xylene diisocyanate;
(II-2) The polyisocyanate component (A) and a polyol component (B) containing 70 to 100% by mass of a polyether polyurethane polyol having a number average molecular weight of 200 to 3000 are mixed,
4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and xylene contained in a total of 100% by mass of the polyisocyanate component (A) and the polyol component (B). A step of preparing an adhesive composition in which the total amount of at least one isocyanate component selected from the group consisting of diisocyanates is 10 to 34% by mass.
(III) A step of applying the ink composition to the transparent substrate 1 and drying or curing to obtain an 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 stacking the base material 2 on the precursor of the adhesive layer.
(VI) A step of curing the precursor of the adhesive layer to form an adhesive layer. It is a manufacturing method of the laminated body which has the transparent base material 1, the ink layer, the adhesive bond layer, and the base material 2 with an oxygen permeability of 100 CC (m ² , 24 hr, 1 atm, 25 ° C.) or less in this order. The manufacturing method of the laminated body containing (I)-(III) and (VII)-(IX).
(I-1) 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 amino group, and the polymer polyol having a number average molecular weight of 400 to 5000 is 100% by mass. Polyurethane polyurea resin containing 5 mass% or more of middle polyester polyol, the total concentration of urethane bonds and urea bonds contained in 1 g of polyurethane polyurea resin is 1.3 to 2.4 mmol / g, and the number average molecular weight is 15000 to 70000 The process of preparing.
(I-2) The polyurethane polyurea resin, vinyl chloride-vinyl acetate copolymer, pigment, and organic solvent are contained, and the total amount of the polyurethane polyurea resin and the vinyl chloride-vinyl acetate copolymer is 100% by mass. And a step of preparing an ink composition containing 5 to 40% by mass of the vinyl chloride-vinyl acetate copolymer.

(II-1) After reacting 4,4′-diphenylmethane diisocyanate with a polyol essentially containing a polyether polyol under an isocyanate group-excess condition,
At least one bifunctional selected from the group consisting of a trimer of a bifunctional isocyanate monomer, a burette in which water is added to the bifunctional isocyanate monomer, and an adduct in which a monoalcohol is added to the bifunctional isocyanate monomer. A modified isocyanate monomer;
If necessary, mix at least one isocyanate component selected from the group consisting of 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and xylene diisocyanate,
A urethane prepolymer (a) having an isocyanate group;
4,4′-diphenylmethane diisocyanate;
At least one bifunctional selected from the group consisting of a trimer of a bifunctional isocyanate monomer, a burette in which water is added to the bifunctional isocyanate monomer, and an adduct in which a monoalcohol is added to the bifunctional isocyanate monomer. A modified product of an isocyanate monomer,
Preparing a polyisocyanate component (A), which may further contain at least one isocyanate component selected from the group consisting of 2,4′-diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and xylene diisocyanate;
(II-2) The polyisocyanate component (A) and a polyol component (B) containing 70 to 100% by mass of a polyether polyurethane polyol having a number average molecular weight of 200 to 3000 are mixed,
4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and xylene contained in a total of 100% by mass of the polyisocyanate component (A) and the polyol component (B). A step of preparing an adhesive composition in which the total amount of at least one isocyanate component selected from the group consisting of diisocyanates is 10 to 34% by mass.

(III) A step of applying the ink composition to the transparent substrate 1 and drying or curing to obtain an ink layer.
(VII) A step of coating the adhesive composition on the substrate 2 to form a precursor of the adhesive layer.
(VIII) A step of overlaying the ink layer on the precursor of the adhesive layer.
(IX) A step of curing the adhesive layer precursor to form an adhesive layer.