KR20180130518A - Laminate and manufacturing method thereof - Google Patents

Abstract

The adhesive composition is coated at a high speed (for example, a coating speed of 200 m / min) using a substrate having excellent gas barrier properties, and a laminate having good appearance of the printed portion is obtained at a low temperature (40 캜) with short aging.
The laminate of the present invention is a laminate having a first substrate, a specific ink layer, a specific adhesive layer and a gas barrier second substrate in this order, wherein the ink layer contains a specific polyurethane polyurea resin and a specific amount of vinyl chloride- (A) is a cured product of an adhesive composition containing a polyisocyanate component (A) and a polyol component (B), and the polyisocyanate component (A) is an isocyanate group Further comprises at least one isocyanate selected from the group consisting of 2,4'-diphenylmethane diisocyanate and trilene diisocyanate, which contains an urethane prepolymer (a) having an isocyanate group and 4,4'-diphenylmethane diisocyanate.

Description

Laminate and manufacturing method thereof

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

Bonding between various plastic films, bonding of a plastic film to a metal evaporated film or a metal foil has been carried out by a dry lamination method using a solvent type adhesive composition of hydroxyl group / isocyanate type. However, in the dry lamination method, special equipment for suppressing and preventing environmental pollution and fire is required by using an adhesive composition containing an organic solvent.

In recent years, there has been a strong demand for durability and shoe molding due to the demand for easy facilities for shoe fabrication for the adhesive composition.

For example, Patent Document 1 discloses an adhesive composition for a laminate of a solventless formulation containing a polyol component (1) and a polyisocyanate component (2) comprising two kinds of polyisocyanate compounds. In addition, reference numerals (1) and so on in the document are notations described in the respective documents and do not coincide with those of the present invention (the same shall apply hereinafter).

Patent Document 2 discloses a polyurethane resin composition containing a polyol component (1) and a polyisocyanate component (2) containing a trifunctional polyisocyanate compound as essential components and having a branching point concentration in a specific range and having a molar number of hydroxyl groups: 1 to 1: 3. ≪ / RTI >

Patent Document 3 discloses a solventless adhesive composition containing a polyol component (A) and an isocyanate component (B) essentially comprising 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 diameter.

Patent Document 5 discloses a polyisocyanate composition comprising a polyisocyanate component (A) and a polyol component (B), wherein the polyisocyanate component (A) is 2,4'-diphenylmethane diisocyanate (a1), 4,4'- Wherein the polyol component (B) is a reaction product obtained by reacting a polyol essentially comprising a diisocyanate (a2) and a polyether polyol (a3) under an isocyanate group in an excessively large amount and the polyol component (B) is a polyester diol having a number average molecular weight of 500 to 3000 (B2) or triol (b3) having a number-average molecular weight of 50 or more and less than 500. The adhesive composition according to claim 1, wherein the diol (b2) or triol (b3)

In Claim 2 of Patent Document 6, the outer polyethylene terephthalate film layer (F1), the printing ink drying coat layer (P), the dry coat layer (C) of the coating resin, the solventless adhesive layer A metal foil M, and a built-in plastic film layer F2 in this order.

Patent Document 7 discloses a two-component curing type non-solvent adhesive composition containing a crystalline polyol component in a specific amount in the total amount of the polyol component (A) and the polyisocyanate component (B).

Patent Document 8 discloses an adhesive composition comprising a specific polyisocyanate component (A) containing a urethane prepolymer and a crude MDI based on a polyether polyol as a raw material, and a specific polyol component (B) containing a polyester diol as an essential component have.

Japanese Unexamined Patent Application Publication No. 8-60131 Japanese Unexamined Patent Application Publication No. 2003-96428 Japanese Patent Application Laid-Open No. 2006-57089 Japanese Patent Application Laid-Open No. 2011-162579 Japanese Patent Application Laid-Open No. 2014-159548 Japanese Patent Application Laid-Open No. 2010-280122 Japanese Patent Application Laid-Open No. 2002-249745 Japanese Patent No. 5812219

The laminate as the packaging material has a laminated structure in which a printing ink layer is formed on the major surface (hereinafter also referred to as the rear surface or rear side) of the transparent substrate at the specific surface side thereof and the adhesive layer and the substrate are laminated on the ink layer in this order . The printing ink layer is visible through the main surface (hereinafter also referred to as the surface or side) on the transparent substrate surface side. The printing ink layer is formed on a part of the transparent substrate in addition to the aspect that the printing ink layer is provided on the entire surface with respect to the transparent substrate. The printing ink layer is composed of a single layer or a laminate of several ink layers. The portion where the printing ink layer is provided may be classified as the non-ink portion.

The adhesive composition that does not contain a solvent has an advantage that the running cost is good due to energy saving because there is no discharge of the solvent without the drying process. And there is no fear that the solvent will remain in the laminate after the plastic films are brought into contact with each other or in the laminate after the plastic film and the metal foil or the metal vapor deposition layer are brought into contact with each other. However, when a laminate is formed from a packaging material using a solvent-resistant adhesive composition and a substrate having a metal vapor deposition layer on the film and a highly gas barrier material (hereinafter also referred to as a barrier material), the appearance There is a problem that defects easily occur.

Patent Documents 1 to 4 disclose that the reaction is relatively mild as a polyisocyanate component, specifically, the use of an alicyclic polyisocyanate component and an aliphatic polyisocyanate component. However, in the case of the polyisocyanate component having relatively mild reaction, the aging step requires 2 to 5 days at 40 to 50 DEG C, which results in a problem of low productivity. Further, Patent Documents 1 to 4 do not describe improvements in appearance defects of ink portions. The term " aging step "means " a step of advancing the curing of the adhesive layer ".

Patent Document 5 discloses an adhesive composition having good adhesive performance and good port life even under the humidity in which moisture and reactivity are controlled. However, Patent Document 5 does not mention improvement of the appearance defect of the ink portion.

Patent Document 6 discloses that when a printing ink drying coat layer (P) is formed between an outer polyethylene terephthalate film layer (F1) and a dry coat layer (C) of a coat resin, a dry coat layer (C) The coat resin constituting the ink is intended to improve the appearance of the ink portion by using a binder for printing ink (see paragraphs [0013] and [0014]). However, the processing speed, specifically the adhesive coating speed, which is specifically shown in the examples, is as low as only 10 m / min. Since the solventless adhesive composition is a solvent-free agent, up to now, the coated surface becomes rough when the coating speed is increased, so that it is difficult to improve both the coating speed and the appearance. From the viewpoint of productivity improvement, a laminate having good appearance of the ink portion at a coating speed similar to that of the solvent-type adhesive composition, for example, at a coating speed of about 200 m / min, is also demanded in a solventless adhesive composition.

On the other hand, Patent Document 7 discloses that the appearance of the ink portion is improved at a coating speed of 200 m / min by using a solvent-free adhesive composition containing a specific amount of crystalline polyester. However, since crystalline polyester is used, For example, at a low temperature aging of 40 캜, defective appearance can not be improved.

In Patent Document 8, it is described that a laminate excellent in appearance is obtained by coating at a speed of 200 m / min or more and aging at a low temperature in a short time, but improvement of the appearance of the printing portion is desired.

It is an object of the present invention to provide a method for producing a pressure-sensitive adhesive sheet having a high gas barrier property (a substrate having an oxygen permeability of 100 cc / (m 2 · day · atm) at 25 ° C.) (For example, 40 占 폚) and aging in a short period of time to provide a laminate having a good printed appearance.

The present invention has been accomplished on the basis of the discovery that it is possible to solve the problems of the present invention in the following embodiments, thereby completing the present invention.

 That is, one embodiment of the present invention relates to a method of manufacturing a light-emitting device, which comprises a first substrate having visible light transmittance, a specific ink layer, a specific adhesive layer, and a second substrate having an oxygen transmission coefficient of 100 cc / (m 2 · day · atm) .

 That is, the ink layer satisfies all the conditions (1) to (5) below and the adhesive layer satisfies the conditions (11) to (15) below.

(1) The ink layer is a dried or cured product of an ink composition containing a polyurethane polyurea resin, a vinyl chloride-vinyl acetate copolymer, a pigment and an organic solvent.

(2) 5 to 40% by mass of the vinyl chloride-vinyl acetate copolymer in a total of 100% by mass of the polyurethane polyurea resin and the vinyl chloride-vinyl acetate copolymer.

(3) The polyurethane polyurea resin has a polyurethane block having a structural unit derived from a high molecular weight polyol having a number average molecular weight of 400 to 5000 and a structural unit derived from a polyisocyanate compound and a chain extension unit derived from a compound having an amino group Wherein the polyurethane block and the chain elongating unit are bonded by a urea bond and include 5% by mass or more of the polyester polyol in 100% by mass of the polymer polyol having a number average molecular weight of 400 to 5000.

(4) The polyurethane polyurea resin has a mass average molecular weight of 15,000 to 70,000.

(5) The total concentration of urethane bond and urea bond 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) comprises a urethane prepolymer (a) having an isocyanate group and 4,4'-diphenylmethane diisocyanate, wherein 2,4'-diphenylmethane diisocyanate and triphenyl diisocyanate And at least one isocyanate selected from the group consisting of

(13) The process for producing a urethane prepolymer as described in any one of (1) to (10), wherein the isocyanate group-containing urethane prepolymer (a) comprises 4,4'-diphenylmethane diisocyanate A reaction product of an isocyanate component further containing one kind of component and a polyol in which a polyether polyol is essential

or

A reaction product of 4,4'-diphenylmethane diisocyanate and a polyol, and a reaction product of an isocyanate component and at least one polyol selected from the group consisting of 2,4'-diphenylmethane diisocyanate and trilene diisocyanate , And at least one of the polyols is a polyether polyol.

(14) The polyol component (B) essentially contains a polyester polyol having a number average molecular weight of 500 to 3000.

(15) The total amount of 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate and styrene diisocyanate contained in 100% by mass of the adhesive composition is 10 to 34% by mass.

Herein, "having visible light transmittance" means that the ink layer bonded to the first base material can be visually recognized through the first base material, and includes colorless transparency as well as colorless transparency. The laminate may be laminated with other layers within the scope of the present invention. The oxygen permeability in this specification is measured at 25 占 폚. (100 m 2 · day · atm) is 987 mL / (m 2 · day · MPa) since the oxygen permeability is 1.87 mL / (m 2 · day · MPa). The term "dried composition or cured product of the ink composition" refers to an ink layer obtained by drying a layer formed using an ink composition or an ink layer formed by curing a layer of an ink composition. The term " chain extending unit "refers to an end blocker and / or chain extender.

Another embodiment of the present invention relates to a laminate in which the pigment contained in the ink layer is titanium dioxide.

In another embodiment of the present invention, the second substrate is a transparent film, and a metal deposition layer is laminated on one main surface of the transparent film. The metal vapor deposition layer is in contact with the adhesive layer will be.

Here, "transparent film" refers to a film having visible light transmittance, and is defined similarly to the first base layer described above.

Further, another embodiment of the present invention is a method for producing a second substrate having visible light transmittance, a specific ink layer, a specific adhesive layer, and a second substrate having an oxygen permeability of 100 cc / (m 2 · day · atm) , And relates to a method for producing a laminate including the following steps (I) to (VI).

(I-1) a high molecular polyol having a number average molecular weight of 400 to 5000, and a reaction product with a polyisocyanate compound and a compound having an amino group, wherein the polyester polyol is contained in an amount of not less than 5% by weight And preparing a polyurethane polyurea resin having a total concentration of urethane bond and urea bond of 1.3 to 2.4 mmol / g and a number average molecular weight of 15000 to 70000 contained in 1 g of the polyurethane polyurea resin.

(I-2) A polyurethane resin composition comprising the polyurethane polyurea resin, a vinyl chloride-vinyl acetate copolymer, a pigment and an organic solvent, the polyurea polyurea resin and the vinyl chloride-vinyl acetate copolymer in a total amount of 100% And 5 to 40 mass% of a vinyl-vinyl acetate copolymer.

(II-1) a urethane prepolymer (a) having an isocyanate group, and 4,4'-diphenylmethane diisocyanate, and is selected from the group consisting of 2,4'-diphenylmethane diisocyanate and trilene diisocyanate Preparing a polyisocyanate component (A) further comprising at least one isocyanate component,

The urethane prepolymer (a)

An isocyanate component containing 4,4'-diphenylmethane diisocyanate as essential components and further containing at least one member selected from the group consisting of 2,4'-diphenylmethane diisocyanate and trilene diisocyanate, and a polyether polyol The requisite polyol may be reacted with an excess of isocyanate group

or

Wherein at least one kind of isocyanate component selected from the group consisting of 2,4'-diphenylmethane diisocyanate and trilene diisocyanate and a polyol having essential polyether polyol as essential components, wherein 4,4'-diphenylmethane diisocyanate is essential, Is reacted with an excess of isocyanate group, respectively, and then mixed.

(II-2) The polyisocyanate component (A) and the polyol component (B) essentially containing a polyester polyol having a number average molecular weight of 500 to 3000 are mixed,

The total amount of 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate and trilene diisocyanate contained in the total of 100 mass% of the polyisocyanate component (A) and the polyol component (B) And 10 to 34% by mass of the adhesive composition.

(III) A step of coating the ink composition on the first substrate and drying or curing the ink composition to obtain the ink layer.

(IV) A step of coating the adhesive composition on the ink layer to form a precursor of the adhesive layer.

(V) a step of overlapping the second substrate on the precursor of the adhesive layer.

(VI) A step of curing the precursor of the adhesive layer after the step (V) to form the adhesive layer.

In another embodiment of the present invention, there is provided a method for manufacturing a light emitting device, comprising the steps of: forming a first substrate having visible light transmittance, a specific ink layer, a specific adhesive layer, and a second substrate having an oxygen permeability of 100 cc / (m 2 · day · atm) And a method for manufacturing another laminated body. That is, the present invention relates to a method for producing a laminate including the following steps (I) to (III), (VII) to (IX).

(I-1) a high molecular polyol having a number average molecular weight of 400 to 5000, and a reaction product with a polyisocyanate compound and a compound having an amino group, wherein the polyester polyol is contained in an amount of not less than 5% by weight And preparing a polyurethane polyurea resin having a total concentration of urethane bond and urea bond of 1.3 to 2.4 mmol / g and a number average molecular weight of 15000 to 70000 contained in 1 g of the polyurethane polyurea resin.

(I-2) A polyurethane resin composition comprising the polyurethane polyurea resin, a vinyl chloride-vinyl acetate copolymer, a pigment and an organic solvent, the polyurea polyurea resin and the vinyl chloride-vinyl acetate copolymer in a total amount of 100% And 5 to 40 mass% of a vinyl-vinyl acetate copolymer.

(II-1) a urethane prepolymer (a) having an isocyanate group, and 4,4'-diphenylmethane diisocyanate, and is selected from the group consisting of 2,4'-diphenylmethane diisocyanate and trilene diisocyanate Preparing a polyisocyanate component (A) further comprising at least one isocyanate component,

The urethane prepolymer (a)

An isocyanate component containing 4,4'-diphenylmethane diisocyanate as essential components and further containing at least one member selected from the group consisting of 2,4'-diphenylmethane diisocyanate and trilene diisocyanate, and a polyether polyol The requisite polyol may be reacted with an excess of isocyanate group

or

Wherein at least one kind of isocyanate component selected from the group consisting of 2,4'-diphenylmethane diisocyanate and trilene diisocyanate and a polyol having essential polyether polyol as essential components, wherein 4,4'-diphenylmethane diisocyanate is essential, Is reacted with an excess of isocyanate group, respectively, and then mixed.

(II-2) The polyisocyanate component (A) and the polyol component (B) essentially containing a polyester polyol having a number average molecular weight of 500 to 3000 are mixed,

The total amount of 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate and trilene diisocyanate contained in the total of 100 mass% of the polyisocyanate component (A) and the polyol component (B) And 10 to 34% by mass of the adhesive composition.

(III) A step of coating the ink composition on the first substrate and drying or curing the ink composition to obtain the ink layer.

(VII) A step of coating the adhesive composition on the second base material to form a precursor of the adhesive layer.

(VIII) A step of overlapping the ink layer on the precursor of the adhesive layer.

(IX) A step of curing the precursor of the adhesive layer after the step (VIII) to form the adhesive layer.

According to the present invention, when a substrate having excellent gas barrier properties (a substrate having an oxygen permeability at 25 ° C of 100 cc / (m 2 · day · atm) or less) is used, the adhesive composition For example, at a low temperature (40 占 폚) and aging for a short period of time to provide a laminate having a good printed appearance.

Hereinafter, an example of an embodiment to which the present invention is applied will be described. It is needless to say that other embodiments are also included in the scope of the present invention as long as the spirit of the present invention is satisfied. In the present specification, specific numerical values are values obtained by the method disclosed in the embodiment or the embodiment. The numerical values "A to B" specified in this specification are the range including the numerical value A and the numerical value B, and larger than the numerical value A and smaller than the numerical value B. The various components in the present specification may be used singly or in combination of two or more species, unless specifically indicated otherwise.

The laminate according to the present embodiment is formed by laminating a first base material having visible light transmittance, an ink layer, an adhesive layer, and a second base material having an oxygen transmission rate of 100 cc / (m 2 · day · atm) or less at 25 ° C in this order .

<Ink Layer>

The ink layer is a dried or cured ink composition. The ink composition contains a polyurethane polyurea resin, a vinyl chloride-vinyl acetate copolymer, a pigment and an organic solvent, as described above.

First, the polyurethane polyurea resin contained in the ink composition will be described. The polyurethane polyurea resin of the present embodiment is a reaction product of a urethane prepolymer having an isocyanate group and a compound having an amino group, which is obtained by reacting a high molecular weight polyol and a polyisocyanate compound. In other words, the polyurethane polyurea resin is a chain extending unit derived from a compound having a structural unit derived from a high molecular polyol and a structural unit derived from a polyisocyanate compound (corresponding to a residue of a urethane prepolymer) and an amino group Corresponding to the residue of the compound having an amino group). And the polyurethane block and the chain extension unit are bonded by a urea bond.

The polymer polyol has a well-known polymer polyol for gravure ink and flexo ink, and can be obtained by a polymerization reaction, a condensation reaction, or a natural product. Most of the polymer polyols have a number average molecular weight of 400 to 10000, but the polyurethane polyurea resin of the present embodiment essentially contains a structural unit derived from a high molecular weight polyol having a number average molecular weight of 400 to 5,000. By including the structural unit derived from the high molecular weight polyol having a number average molecular weight of 400 or more, since the polyurethane polyurea resin has appropriate flexibility, the leveling property at the time of printing the ink composition on the first substrate is excellent, The appearance is improved. The incorporation of a structural unit derived from a high molecular weight polyol having a number average molecular weight of 5,000 or less improves the cohesive force of the obtained ink layer and suppresses the penetration of the isocyanate monomer into the ink layer in the adhesive composition so that the appearance of the laminate and the laminate strength are improved do.

The structure of the polymer polyol of the present embodiment may be any of various known high molecular polyols commonly used in the production of polyurethane resin and may be used singly or in combination of two or more. (1) a polymer or copolymer of polyether polyols such as methylene oxide, ethylene oxide, propylene oxide, tetrahydrofuran and the like;

Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-ethyl- Butene diol, 1,4-butylene diol, diethylene glycol, triethylene glycol, diethylene glycol, 1,4-butylene glycol, Saturated or unsaturated low molecular weight polyhydric alcohols such as dipropylene glycol, glycerin, trimethylol propane, trimethylol ethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, sorbitol and pentaerythritol And polyhydric alcohols such as adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, trimellitic acid and pyromellitic acid Polyester polyols (2) obtainable by dehydration condensation or polymerization of carboxylic acids or anhydrides thereof;

(3) polyester polyols obtainable by ring-opening polymerization of lactones such as cyclic ester compounds, for example, polycaprolactone, polyvalerolactone and poly (beta -methyl- gamma -valerolactone);

Polycarbonate polyols (4) obtainable by reacting the low-molecular polyhydric alcohols and the like with, for example, dimethyl carbonate, diphenyl carbonate, ethylene carbonate, phosgene and the like;

Polybutadiene glycols (5);

Glycols (6) obtained by adding ethylene oxide or propylene oxide to bisphenol A;

 An acrylic polyol obtained by copolymerizing acrylic acid, methacrylic acid or an ester thereof with at least one hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, etc., or a corresponding methacrylic acid derivative or the like in a molecule 7).

 Among the high molecular polyols, the polyester polyols are particularly excellent in terms of the adhesion of the first base material of the ink layer and the solubility of the ink composition in the solvent. The polyurethane polyurea resin of this embodiment contains 5% by mass or more of polyester polyols in 100% by mass of a high molecular weight polyol having a number average molecular weight of 400 to 5,000. By containing not less than 5% by mass of the polyester polyol, penetration of the adhesive component into the resulting ink layer can be suppressed and the appearance of the laminate and the strength of the laminate 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.

Examples of the polyester polyols include polyols having at least one branched structure selected from 2-methyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol or 3-methyl- The polyester polyol that can be obtained by polymerizing diol and adipic acid has a branched structure and therefore is excellent in adhesion to a substrate and in solubility. In particular, a polyester polyol obtainable 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 components, a polymer polyol other than one or more polyester polyols may be used in combination. The polymer polyol used in combination may have high adhesion to the first base material, Polyether polyols excellent in solubility are preferable. As the polyether polyols, polymers of propylene oxide having suitable flexibility in terms of adhesion to a substrate are preferable.

In addition to the polymer polyol, a low-molecular polyol having a number average molecular weight of 400 or less may optionally be contained. As the structure of the low molecular weight polyol, various known low molecular weight polyols generally used for the production of polyurethane resin may be used, and one or more kinds of them may be used in combination. For example, there may be mentioned ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, , 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1,5-pentanediol, hexanediol, octanediol, 1,4-butanediol, 1,4- Saturated or unsaturated low molecular weight compounds such as triethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, sorbitol and pentaerythritol Low molecular diols containing carboxylic acids such as polyols, dimethylolbutanoic acid and dimethylolpropionic acid, and low molecular triols such as trimethylolpropane. By using these low-molecular diols, adjustment of the urethane bond density and introduction of functional groups to the polyurethane polyurea resin are facilitated.

Examples of the polyisocyanate compound used for forming the polyurethane polyurea resin include various known aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates and the like commonly used in the production of polyurethane resins. For example, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzylisocyanate, dialkyldiphenylmethane diisocyanate, tetra 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, cyclohexane-1,4-diisocyanate, xylene diisocyanate, isophorone diisocyanate, dimethyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate , 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate , m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylenediisocyanate, bis-chloromethyl-diphenylmethane-diisocyanate, 2,6-diisocyanate-benzyl chloride, and dimer acid And dimer diisocyanate in which a carboxyl group is converted into an isocyanate group. These diisocyanate compounds may be used alone or in combination of two or more.

Of these polyisocyanate compounds, isophorone diisocyanate, tolylenediisocyanate 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 a terminal blocking agent for stopping the reaction between the chain extender and the polyurethane polyurea resin for the purpose of increasing the molecular weight of the urethane prepolymer.

Examples of the chain extender include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4'-diamine, and the like. Examples of the chain extender capable of adding a hydroxyl group to the side chain of the polyurethane polyurea resin include 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, 2-hydroxyethylpropylenediamine, di-2- Hydroxyethyl ethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, etc., Can also be used. The chain extender may be used alone or in combination of two or more. It is preferable to use isophoronediamine and 2-hydroxyethylethylenediamine in combination in view of improving the workability at the time of printing because the resulting ink composition exhibits excellent solubility in solvents.

Examples of the terminal blocking agent include monoethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol, tri (hydroxymethyl) aminomethane , 2-amino-2-ethyl-1,3-propanediol, and other monoamines having a hydroxyl group. In addition, monoamine type amino acids such as glycine, alanine, glutamic acid, taurine, aspartic acid, aminobutyric acid, valine, aminocaproic acid, aminobenzoic acid, aminoisophthalic acid and sulfamic acid are also exemplified. By using monoamines having a hydroxyl group such as monoethanolamine, a hydroxyl group can be added to the terminal of the polyurethane polyurea resin.

In addition to the compound having an amino group, a monovalent active hydrogen compound may be used as the end blocker. Examples of such a compound include alcohols such as ethanol and isopropyl alcohol.

The polyurethane polyurea resin of the present embodiment is obtained by reacting a urethane prepolymer having an isocyanate group at a terminal thereof with a compound having an amino group. That is, a polyol and polyisocyanate compound containing a high molecular polyol are reacted with a solvent inert to the isocyanate group, if necessary, or, if necessary, a catalyst at a temperature of 10 to 100 ° C, and a urethane To prepare a prepolymer. The urethane prepolymer and the compound having an amino group are then reacted at 10 to 80 캜.

The method of reacting the urethane prepolymer with the compound having an amino group includes a method of slowly dropping a solution of a compound having an amino group in a urethane prepolymer solution and a method of dropping a urethane prepolymer solution in a solution of a compound having an amino group. .

The polyurethane polyurea resin of the present embodiment has a mass average molecular weight of 15,000 to 70,000, preferably 30,000 to 60,000.

When the mass average molecular weight is 15,000 or more, the pigment dispersibility is excellent, and the resulting ink composition is excellent in color development and the cohesive force of the ink layer is also enhanced. Further, since it exhibits a high cohesive force, penetration of the adhesive composition into the ink layer can be suppressed. Therefore, the appearance of the laminate and the laminate strength are good.

The weight average molecular weight is not more than 70000, and the resulting ink composition is excellent in leveling property when printing with the first base material, and a flat ink layer surface can be obtained without irregularities due to leveling defects. Therefore, gaps and / or bubbles are hardly generated at the interface between the ink layer and the adhesives, and the appearance of the laminate is improved. In addition, the working efficiency in the printing process using the obtained ink composition is also improved.

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

The polyurethane polyurea resin of the present embodiment has a total concentration of urethane bond and urea bond of 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 laminated on the resulting ink layer is less likely to penetrate, and the appearance of the laminate becomes better. When it is 2.4 mmol / g or less, the solubility in the solvent is improved and the leveling property of the obtained ink composition becomes good. As a result, a more uniform ink layer can be formed, and the appearance of the laminate becomes better.

The urethane bond concentration can be controlled by one of the number average molecular weight of all the polyols used in the reaction for obtaining the urethane prepolymer or the NCO / OH ratio, which is the molar ratio of the hydroxyl group to the isocyanate group in the reaction for obtaining the urethane prepolymer .

The urea bond concentration can be controlled by the number average molecular weight of the compound having all the amino groups used or the NCO / NH ratio which is the molar ratio of the primary or secondary amino group in the compound having an isocyanate group and an amino group in the urethane prepolymer. In the polyurethane resin of the present embodiment, the total concentration of the urethane bond and the urea bond is 1.3 to 2.4 mmol / g, the concentration of each of the urethane bond and the urea bond is preferably in the range of 0.5 to 1.2 mmol / g Do.

Next, the vinyl chloride-vinyl acetate copolymer (hereinafter also referred to as CA) contained in the ink composition of the present embodiment will be described. The ink composition of the present embodiment contains a vinyl chloride-vinyl acetate copolymer. The vinyl chloride-vinyl acetate copolymer may have a vinyl chloride moiety and a vinyl acetate moiety as essential components, and may have a vinyl alcohol-modified moiety or a maleic acid-modified moiety. The vinyl chloride-vinyl acetate copolymer preferably contains 85 to 95% by weight of the vinyl chloride moiety and 1 to 15% by weight of the vinyl acetate moiety in 100% by weight of the vinyl chloride-vinyl acetate copolymer, and the molecular weight of the vinyl chloride- Range. Vinyl chloride-vinyl acetate copolymer is commercially available and is commercially available, for example, from Solvain C, CL, CH, CN, CNL, C5R, A, AL, TA5R, TA3, TAO, M5 manufactured by Nissin Chemical Industry Co., / 45, H14 / 36, H15 / 42, H40 / 43, H40 / 50, H20 / 45, E15 / 45M, H30 / 48M and H15 / 45M.

The vinyl chloride-vinyl acetate copolymer is excellent in compatibility with other components in the polyurethane polyurea resin and the ink composition, and is therefore suitable for producing a printed article having good appearance without pinholes and the like. Furthermore, penetration of the adhesive composition component into the ink layer can be suppressed by the chemical resistance of the vinyl chloride moiety. Further, since the plasticity of the vinyl acetate moieties increases the adhesion of the ink layer to the first substrate, a laminate having good laminate strength can be obtained.

It is important that the ink composition of the present embodiment contains 5 to 40% by mass of a vinyl chloride-vinyl acetate copolymer in 100% by mass of the combined solid content of the polyurethane polyurea resin and the vinyl chloride-vinyl acetate copolymer, %. When the content is 5% by mass or more, it is difficult for the adhesive to penetrate the ink layer, and the appearance of the laminate becomes good. On the other hand, when the content is 40 mass% or less, the laminate strength of the laminate becomes favorable.

Among vinyl chloride-vinyl acetate copolymers, a vinyl chloride-vinyl acetate copolymer containing a hydroxyl group is obtained by reacting a solvent other than toluene (hereinafter also referred to as non-toluene) with a ketone such as methyl ethyl ketone or methyl isobutyl ketone The solubility in a solvent other than a solvent (hereinafter also referred to as a nonketone) is particularly excellent. It is preferable that an ink composition is prepared using non-toluene or / and a non-ketone solvent, and when the ink composition is printed, it contains the vinyl chloride-vinyl acetate copolymer containing the hydroxyl group. Solvent A, AL, TA5R, TAO and the like can be exemplified as the vinyl chloride-vinyl acetate copolymer containing a hydroxyl group.

Various resins other than the polyurethane polyurea resin and vinyl chloride-vinyl acetate copolymer described above may be used in combination with the ink composition of the present embodiment, depending on the use and the base material. Examples of the resin to be used include polyurethane resins other than the above-mentioned materials, polyurethane resins, polyvinyl chloride-acrylate copolymers, chlorinated polypropylene resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, polyamide resins, But are not limited to, cellulose resin, acrylic resin, acrylic resin, polyester resin, alkyd resin, polyvinyl chloride resin, rosin resin, rosin-modified maleic resin, terpene resin, phenol modified terpene resin, ketone resin, And modified resins thereof. These resins may be used singly or in combination of two or more, and the content thereof is preferably 0.5 to 20% by mass based on 100% by mass of the solid content of the ink composition.

The ink composition of this embodiment may use an inorganic pigment and an organic pigment as the pigment. It is preferable that the pigment is contained in an amount sufficient to ensure the concentration of the printed matter, that is, in a proportion of 1 to 50 mass% of 100 mass% of the ink composition. These pigments may be used alone or in combination of two or more.

The organic pigments include those used in general inks, paints, recording materials and the like. For example, there may be mentioned azo, phthalocyanine, anthraquinone, perylene, perinone, quinacridone, thioindigo, dioxazine, isoindolinone, quinophthalone, azomethine, Maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, and the like. As the blue ink, it is preferable to use CI Pigment No Yellow 83 in terms of cost and light resistance for copper phthalocyanine and transparent yellow ink.

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

 The ink layer is composed of a single layer or a multilayer, and may be formed of any layer depending on the application. In general, a multicolor ink layer is formed and then a white ink layer is laminated in many cases. In this case, the white ink layer comes into direct contact with the adhesive layer stacked on the upper layer. Therefore, suppressing the penetration of the adhesive layer component into the white ink layer is most effective for improving the appearance of the layered product. Therefore, it is preferable to use a white inorganic pigment as the pigment of the ink layer. Among them, it is more preferable to use titanium dioxide. Since titanium dioxide is excellent in chemical resistance, penetration of the adhesive into the white ink layer can be suppressed, and it is suitable for obtaining a laminate having good appearance in terms of reducing power and hiding power. The titanium dioxide is preferably subjected to a surface treatment with an inorganic oxide. Examples thereof include a silica treatment, an alumina treatment, and a silica / alumina treatment.

 The ink composition of the present embodiment may be used as a one-pack type ink composition, but it may be used as a two-pack type ink composition by adding a conventional isocyanate curing agent for the purpose of further improving heat resistance and water resistance according to use of the laminate. Examples of the isocyanate-based curing agent include adduct-type polyisocyanates (adducts), biuret-type polyisocyanates (diphenylmethane diisocyanate) (TDI), diphenylmethane diisocyanate (MDI), and hexamethylene diisocyanate Isocyanurate type polyisocyanate (isocyanurate form), and the like can be used. For example, an adduct obtained by reacting 1 mole of trimethylolpropane with 3 moles of HDI, a burette obtained by reacting 1 mole of water with 3 moles of HDI, an isocyanurate obtained by cyclic trimerization of HDI, and the like . When used as a two-component printing ink, the addition amount of the polyisocyanate curing agent is preferably from 3 to 30% by mass based on 100% by mass of the solid content in the ink composition.

 Examples of the organic solvent used in the ink composition of the present embodiment include esters such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate, propylene glycol monoethyl ether acetate and propylene glycol monomethyl ether acetate, , Alcohol solvents such as normal propanol, isopropyl alcohol, normal butanol, propylene glycol monoethyl ether and propylene glycol monomethyl ether, and hydrocarbon solvents such as methylcyclohexane and ethylcyclohexane. From the viewpoint of the recent working environment, there is a demand to exclude aromatic organic solvents such as toluene and xylene, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and the ink composition of this embodiment is preferably used do.

The ink composition of the present embodiment can be produced by dissolving and / or dispersing a resin, a pigment, and the like in an organic solvent. As a specific example, a pigment dispersion in which a pigment, a polyurethane polyurea resin, a vinyl chloride-vinyl acetate copolymer and other resins, and other compounds as required are dispersed in an organic solvent can be used , And the ink composition can be prepared by adding the remaining polyurethane polyurea resin, vinyl chloride-vinyl acetate copolymer, other resin, organic solvent, and other compounds as necessary to the obtained pigment dispersion. The process of obtaining a pigment dispersion is referred to as a kneading process, a step of blending a polyurethane polyurea resin, a vinyl chloride-vinyl acetate copolymer and other resins, an organic solvent and other compounds as needed into the resulting pigment dispersion, ) Process.

A dispersant may be used in combination to stably disperse the pigment in an organic solvent. As the dispersing agent, surfactants such as anionic, nonionic, cationic, and zwitterionic surfactants can be used. The dispersing agent is preferably contained in the ink composition at 0.01 mass% or more with respect to the total mass of the ink from the viewpoint of ink storage stability, and 5 mass% or less from the viewpoint of lamination suitability. Further, it is more preferable that it is contained in the range of 0.05 to 2% by mass.

The particle size distribution of the pigment of the pigment dispersion can be adjusted by appropriately adjusting the size of the pulverizing medium of the dispersing machine, the filling rate of the pulverizing medium, the dispersion processing time, the discharge speed of the pigment dispersion, and the viscosity of the pigment dispersion. As the dispersing device, for example, a roller mill, a ball mill, a pebble mill, an attritor, a sand mill or the like commonly used can be used.

If bubbles or unexpected large particles are contained in the ink composition, it is preferable to remove them by filtration or the like because the quality of the printed matter is lowered. The filter may be any known filter.

The viscosity of the ink composition produced in the above manner is preferably 10 mPa · s or more from the viewpoint of preventing the sedimentation of the pigment and dispersing it appropriately and in the range of 1000 mPa · s or less from the viewpoint of production efficiency of the ink composition or printing. In addition, the viscosity is the viscosity measured at 25 占 폚 in a B-type viscometer manufactured by Tomekk.

<Adhesive Layer>

The adhesive layer of the present embodiment is a cured product of an adhesive composition comprising a polyisocyanate component (A) and a polyol component (B).

First, the polyisocyanate component (A) will be explained.

Hereinafter, 4,4'-diphenylmethane diisocyanate may be referred to as 4,4'-MDI, 2,4'-diphenylmethane diisocyanate as 2,4'-MDI, and trilene diisocyanate as TDI have.

The polyisocyanate component (A) further comprises an isocyanate compound which is at least one selected from the group consisting of 2,4'-MDI and TDI, and a urethane prepolymer (a) having an isocyanate group and 4,4'-

The urethane prepolymer (a) can be obtained by reacting an isocyanate component and a polyol with an isocyanate group in excess of the conditions, and is characterized in that 4,4'-MDI is essential, and at least one selected from the group consisting of 2,4'-MDI and TDI At least one kind of isocyanate compound selected from the group consisting of 2,4'-MDI and TDI, and a reaction product with a polyol in which a polyether polyol is essential and an isocyanate component including one kind, and 4,4'- Wherein each of the components and at least one of the polyols is a polyether which is a polyether polyol.

 That is, the urethane prepolymer (a) used in the present embodiment includes (a1) to (a6).

(a1) a reaction product of 4,4'-MDI and a polyol comprising 2,4'-MDI and a polyether polyol.

(a2) a reaction product of 4,4'-MDI and a polyol comprising TDI and a polyether polyol.

(a3) the reaction product of 4,4'-MDI and 2,4'-MDI and a polyol comprising TDI and a polyether polyol.

(a4) a mixture of a reaction product of 4,4'-MDI and a polyol and a reaction product of 2,4'-MDI and a polyol.

(a5) a mixture of a reaction product of 4,4'-MDI and a polyol and a reaction product of TDI and a polyol.

(a6) a mixture of a reaction product of 4,4'-MDI and a polyol, a reaction product of 2,4'-MDI and a polyol, and a reaction product of TDI and a polyol.

In the case of (a4) to (a6) in which various reaction products are mixed, the polyether polyol may be contained in at least one kind of reaction product among the polyols used.

That is, for example, (a4) includes the following aspects.

(a4-1) A mixture of a reaction product of 4,4'-MDI and a polyol essentially comprising a polyether polyol, and a reaction product of a polyol other than a polyether polyol and 2,4'-MDI.

(a4-2) A mixture of a reaction product of a 4,4'-MDI and a polyol other than a polyether polyol, and a reaction product of a polyol essentially comprising 2,4'-MDI and a polyether polyol.

(a4-3) A mixture of a reaction product of 4,4'-MDI and a polyol essentially comprising a polyether polyol, and a reaction product of a polyol essentially consisting of 2,4'-MDI and a polyether polyol.

The "polyol containing a polyether polyol as essential" may be a polyether polyol alone or a combination of a polyether polyol and a polyol other than the polyether polyol. Thus, (a4-1) includes the following aspects.

(a4-1-1) A mixture of a reaction product of 4,4'-MDI and a polyether polyol, and a reaction product of 2,4'-MDI and a polyol other than a polyether polyol.

(a4-1-2) a reaction product of 4,4'-MDI and a polyether polyol, a reaction product of 4,4'-MDI and a polyol other than polyether polyol, a reaction product of 2,4'-MDI and polyether polyol A mixture of reaction products of other polyols.

The polyol other than the polyether polyol and the polyether polyol may be a single polyol or a mixture of two or more polyols.

In the case of (a1) to (a3), 4,4'-MDI and 2,4'-MDI may be mixed and reacted with a polyether polyol as essential, and each isocyanate may be reacted with a polyether polyol It may be reacted with an essential polyol.

It is also possible to use the reaction products of (a1) to (a3), or to use the mixtures of (a4) to (a6), or to use the mixture of the reaction products of (a1) You may.

The polyol for forming the urethane prepolymer (a) will be described. The polyol contains a polyether polyol as an essential component and may further contain a polyester polyol. The polyether polyol generally has a viscosity lower than that of the polyester polyol in a molten state, and the polyol used for forming the urethane prepolymer in the polyisocyanate component (A), which is a constituent component of the solventless adhesive structure, . By using the polyester polyol in combination with this, the compatibility with the polyol component (B) to be described later can be enhanced, and the cohesive force of the adhesive layer can be increased.

When a polyester polyol is used in combination, it is preferably at most 50 mass% in 100 mass% of the polyol in view of the viscosity of the adhesive composition.

Examples of the polyether polyol include oxirane compounds such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran; and low molecular weight polyols such as water, ethylene glycol, propylene glycol, trimethylol propane, And polyether polyols obtainable by polymerization as an initiator.

The polyether polyol may be a bifunctional or polyfunctional polyfunctional polyol. In addition, a plurality of different functional groups may be used. The polyether polyol preferably has a number average molecular weight of 100 or more and 5,000 or less. It is also possible to use a combination of several different molecular weights.

Polyester polyols include polyester polyols obtainable by reacting a polycarboxylic acid component with a glycol component.

Examples of the polycarboxylic acid component include polycarboxylic acids such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid and sebacic acid, dialkyl esters thereof, and 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, Polyoxyethylene glycols, polyoxypropylene glycols, polytetramethylene ether glycols, and the like, or mixtures thereof.

Examples of the low molecular weight diol include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, Heptane, 2-methyl-1,3-propanediol, and the like, or a mixture thereof.

In the present embodiment, the polyisocyanate component (A) comprises a urethane prepolymer (a) having an isocyanate group and 4,4'-MDI, and is selected from the group consisting of 2,4'-MDI and TDI Lt; / RTI &gt; isocyanate monomer. The isocyanate monomer may be an unreacted isocyanate monomer remaining when the urethane prepolymer (a) is obtained, or may be added after the urethane prepolymer (a) is obtained. The polyisocyanate component (A) preferably has a number average molecular weight of 200 to 800, more preferably 300 or more and 700 or less. The polyisocyanate component (A) contains an urethane prepolymer (a) and also contains an isocyanate monomer, so that the polyisocyanate component (A) has a molecular weight as described above.

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

The ratio of each of 4,4'-MDI, 2,4'-MDI and TDI contained in the polyisocyanate component (A) was 100 mol% in total of 4,4'-MDI, 2,4'-MDI and TDI, MDI is 30 mol% or more and 70 mol% or less, 2,4'-MDI is 30 mol% or more and 70 mol% or less, and TDI is 30 mol% or more and 70 mol% or less.

When the composition ratio of the two kinds of MDI is in the above range, the coated outer appearance of the ink portion of the laminate is improved and the good adhesion performance can be exhibited even if the aging temperature is not controlled at a temperature exceeding 40 캜. When 2,4'-MDI or TDI alone is used, sufficient adhesion performance can not be obtained with short-time aging. On the other hand, if only 4,4'-MDI is used, improvement in appearance of the ink portion of the laminate is insufficient.

Next, the polyol component (B) contained in the adhesive composition of the present embodiment will be described.

The polyol component (B) preferably contains a polyester polyol having a number average molecular weight of 500 to 3,000 and a diol having a number average molecular weight of 50 or more and less than 500, a triol having a number average molecular weight of 50 or more and less than 500 and a triol having a number average molecular weight of 500 to 10000 Of at least one member selected from the group consisting of polyether polyols.

By using a polyester polyol essentially, sufficient adhesion strength can be obtained. A triol having a number average molecular weight of 50 or more and less than 500, a triol having a number average molecular weight of 50 or more and less than 500, and a polyether polyol having a number average molecular weight of 4500 or more and 10000 or less. The strength is improved.

A polyester polyol having a number average molecular weight of 500 to 3,000, which is used as an essential component of the polyol component (B), will be described.

The polyester polyol is obtained by reacting a polycarboxylic acid such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid or sebacic acid, or a dialkyl ester thereof or a mixture thereof with, for example, ethylene glycol, propylene glycol, diethylene glycol, Butylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol Or a mixture thereof, or a lactone such as polycaprolactone, polyvalerolactone and poly (beta -methyl- gamma -valerolactone), which is obtained by ring-opening polymerization of And polyester polyol having a carboxyl group.

Polyester compounds derived from vegetable oils and vegetable oils such as castor oil may also be used.

Representative examples of vegetable oils include vegetable oils such as palm oil, linseed oil, perilla oil, oatissic oil, olive oil, cacao oil, kapok oil, kaeya oil, mustard oil, bank oil, tung oil, kukui oil, walnut oil, , Sunflower seed oil, grape seed oil, almond oil, pine seed oil, cottonseed oil, palm oil, peanut oil, soybean oil, soy sauce oil, safflower oil, camellia oil, rape oil, , Dehydrated castor oil, and the like.

A polyester diol in which a part of the hydroxyl groups in the obtained polyester diol is further reacted with an acid anhydride such as trimellitic anhydride may be used as the polyester diol.

By using a polyester diol to which an acid anhydride is added, adhesion can be improved when it is applied to a sheet-like substrate which is difficult to adhere. The amount of trimellitic anhydride or the like to be added is preferably 0.1 to 5% by mass in 100% by mass of the polyester diol after the reaction. By using the polyester diol having a number average molecular weight within the above range, compatibility with the above polyisocyanate component (A) containing polyether polyurethane as an essential component is improved, a transparent adhesive composition can be obtained, Performance can be exhibited.

Examples of the diol having a number average molecular weight of 50 or more and less than 500 include polyester diols, polyether diols, polyether ester diols, polyester amide diols, acrylic diols, polycarbonate diols, and ethylene glycol, Low molecular weight diols such as glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolheptane and 2-methyl- And mixtures thereof. Of these, from the viewpoint of reactivity, low-molecular diols are preferable.

The polyether diol includes, for example, oxirane compounds such as ethylene oxide, propylene oxide, butylene oxide and tetrahydrofuran such as water, ethylene glycol, propylene glycol and the like as bifunctional low molecular weight polyols as initiators And polyether diols obtainable by polymerization.

Examples of the polyetherester polyols include polyetherester diols obtainable by reacting the above polyether diols with divalent acids such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid and sebacic acid, dialkyl esters thereof, .

The polyester amide diol is obtained by using an aliphatic diamine having an amino group such as ethylenediamine, propylenediamine, hexamethylenediamine or the like as a starting material in the esterification reaction.

Examples of the acrylic diol include acrylic acid hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate and the like, or a corresponding methacrylic acid derivative containing at least one hydroxyl group in a molecule, and acrylic acid, methacrylic acid, And an ester.

Examples of the polycarbonate diol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl- One or more glycols selected from nonane diol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol and 1,4- Dimethyl carbonate, diphenyl carbonate, ethylene carbonate, phosgene and the like.

Triols having a number average molecular weight of 50 or more and less than 500 include polyether triols, castor oil, and low molecular triols such as trimethylol propane and glycerin, or mixtures thereof. Of these, from the viewpoint of reactivity, a low molecular triol or a polyether triol is preferable.

The polyether triol is obtained by polymerizing an oxirane compound such as ethylene oxide, propylene oxide, butylene oxide or tetrahydrofuran with a low molecular weight polyol such as trimethylol propane or glycerin as an initiator Polyether triols.

Examples of the polyether polyol used as the polyether diol having a number average molecular weight of 500 to less than 10000 include oxirane compounds such as ethylene oxide, propylene oxide, butylene oxide and tetrahydrofuran, for example, water, ethylene glycol, And polyether polyols obtainable by polymerizing a low molecular weight polyol such as propylene glycol, trimethylol propane or glycerin with an initiator.

The polyol component (B) comprises 60% by mass or more to 99% by mass or less of a polyester polyol having a number average molecular weight of 500 to 3,000 in 100% by mass of the polyol component (B), a diol having a number average molecular weight of 50 to less than 500, A triol of 50 or more and less than 500 and a polyether polyol having a number average molecular weight of 4500 or more and 10000 or less are preferably contained in an amount of 1% by mass or more and 40% by mass or less. When the combination of diol and triol and polyether diol is within the above range, it is possible to obtain a laminate having a better appearance when coating and aligning at a high speed using a film substrate having high gas barrier properties.

The polyol component (B) may be a polyol having a number average molecular weight of 50 or more and less than 500, a triol having a number average molecular weight of 50 or more and less than 500 and a polyether polyol having a number average molecular weight of 4500 or more and 10000 or less, Lt; RTI ID = 0.0 &gt; polyol &lt; / RTI &gt;

When the number of moles of hydroxyl groups in the polyol component (B) is 100 moles, the adhesive composition of the present embodiment preferably has a molar number of isocyanate groups in the polyisocyanate component (A) of 120 mol or more and 300 mol or less. When the molar number of hydroxyl groups in the polyol component (B) is 100 mol, the molar number of isocyanate groups in the polyisocyanate component (A) is within the above range, whereby even when aging occurs at high humidity, good adhesion can be exhibited.

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

The adhesive composition of the present embodiment may further contain particles having an average particle diameter of 1 x 10 ^-4 to 4 x 10 ^-4 mm. When a film substrate having a high average particle diameter within the above range is used and a film substrate having a high gas barrier property is used to coat and align at high speed, a laminate having a better appearance can be obtained. If the particles are too small, the flow characteristics do not change much and the appearance is not significantly different even when added. Here, the average particle diameter is an average volume diameter, and is a value obtained by a laser light scattering method.

These particles may be either inorganic compounds or organic compounds, or they may be used alone or in combination of two or more.

Examples of the particles of the inorganic compound include aluminum oxide, aluminum silicate, aluminum hydroxide, alumina white, potassium sulfate, zinc oxide, zinc carbonate, magnesium metasilicate alumina, magnesium silicate, magnesium oxide, magnesium hydroxide, Barium carbonate, barium carbonate, barium carbonate, calcium carbonate, calcium hydroxide, calcium oxide, calcium silicate, calcium sulfite, calcium sulfate, titanium dioxide, silica, zeolite, activated carbon, kaolin, talc, Montmorillonite, sepiolite, bentonite, perlite, wollastonite, fluorite, and dolomite. Among them, silica and talc are commonly used.

Examples of the particles of the organic compound include a resin such as a benzoguanamine resin, a silicone resin, a styrene resin, a crosslinked polystyrene, an epoxy resin, a phenol resin, a fluororesin, a polyethylene resin, a polyester resin, a polyimide resin, Polyurethane resin, vinyl acetate copolymer resin, polyphenylene oxide resin, nylon 6, nylon 12, cellulose, acrylic resin, and methacrylic resin. Of these, benzoguanamine resins are commonly used.

The content of the particles is preferably 0.01 to 10 mass parts (C) of particles (C) having an average particle diameter of at least 1 x 10 ^-4 mm and at most 4 x 10 ^-4 mm, in total of 100 parts by mass of the polyisocyanate component (A) Is preferably included. Within this range, the appearance and adhesive strength are improved evenly.

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

It is preferable that the adhesive composition of the present embodiment does not contain a solvent. It is preferable that the adhesive composition is blended at a temperature as low as possible within a range in which fluidity is ensured, and more specifically, blended at 25 ° C or more and 80 ° C or less . The viscosity at 60 캜 immediately after mixing the polyisocyanate component (A) and the polyol component (B) is preferably 50 mPa s to 5000 mPa s, more preferably 50 mPa s to 3000 mPa s.

The term "immediately after mixing" in this embodiment means that it is within 1 minute after homogeneous mixing, and the melt viscosity shows a value obtained by a B-type viscometer. If the melt viscosity at 60 ° C is 5,000 mPa · s or more, it is difficult to ensure good workability because the coating is difficult, and when the coating temperature is 60 ° C. or less, a good appearance of the coating may not be obtained.

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 adhesion performance can not be obtained, the thickness of the coating film is not uniform when coating the adhesive composition on a substrate, .

The adhesive composition of the present embodiment can be used when necessary, such as an antioxidant, an ultraviolet absorber, a hydrolysis inhibitor, an antimicrobial agent, a thickener, a plasticizer, a defoamer, a pigment and a filler.

In order to further improve the adhesion performance, adhesion aids such as silane coupling agents, phosphoric acid, phosphoric acid derivatives, acid anhydrides, and adhesive resins can be used. In order to control the curing reaction, known catalysts, additives and the like can be used.

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 or an ethoxy group can be used.

Examples thereof include chlorosilanes such as vinyltrichlorosilane, aminosilanes such as N- (dimethoxymethylsilylpropyl) ethylenediamine and N- (triethoxysilylpropyl) ethylenediamine, and? -Glycidoxypropyltrimethoxy Silane, epoxy silane such as? -Glycidoxypropyltriethoxy silane, and vinyl silane such as vinyl triethoxy silane.

The addition amount of the silane coupling agent is preferably 0.1 to 5% by mass with respect to the total adhesive composition.

Of the phosphorus oxyacids or derivatives thereof to be used in the present embodiment, the phosphorus oxyacid may be any of those having at least one free oxygen acid, and examples thereof include phosphoric acids such as hypophosphorous acid, phosphorous acid, orthophosphoric acid and hypophosphorous acid, And condensed phosphates such as pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid, and ultraphosphoric acid. The derivatives of phosphorus oxyacids include those obtained by partial esterification of the phosphorus oxyacid with the alcohol in a state in which at least one free oxygen acid is left. These alcohols include aliphatic alcohols such as methanol, ethanol, ethylene glycol and glycerin, aromatic alcohols such as phenol, xylenol, hydroquinone, catechol, and fluoroglucinol. The phosphoric acid or derivative thereof of phosphorus may be used singly or in combination of two or more. The amount of phosphoric acid or derivative thereof to be added is 0.01 to 10% by mass, preferably 0.05 to 5% by mass, more preferably 0.1 to 1% by mass with respect to the total composition.

&Lt; Laminate and method for manufacturing the same &

The laminate of this embodiment and its manufacturing method will be described. The laminate of this embodiment has the first base material, the ink layer, the adhesive layer and the second base material in this order as described above.

Examples of the first substrate include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate (hereinafter also referred to as PET), polycarbonate and polylactic acid, polystyrene resins such as polystyrene, AS resin and ABS resin, nylon, polyamide , Or a film-like or layer-like one composed of polyvinyl chloride, polyvinylidene chloride, cellophane, paper, aluminum or the like or a composite material thereof. The film is applied using the above printing method and dried or hardened by oven drying To obtain a printed matter. The substrate may be subjected to a coating treatment such as a metal oxide or the like on the surface thereof and / or a coating treatment such as polyvinyl alcohol or a surface treatment such as a corona treatment.

The ink layer is a dried or hardened product of the aforementioned ink composition containing a specific polyurethane polyurea resin and a specific amount of a vinyl chloride-vinyl acetate copolymer. The ink layer can be obtained by printing and drying or curing the ink composition on the first substrate. The ink composition can be printed by conventional printing methods such as gravure printing and aniline printing, but it is particularly preferable to perform printing by a gravure printing method. Cylinders used in gravure printing are those known in the art, such as sculpture, corrosion, and the like.

The ink composition diluted with the diluting solvent to a viscosity and a concentration suitable for gravure printing is supplied alone or mixed to each printing apparatus, and after printing, the ink composition is passed through an oven and dried or cured to form an ink layer. The temperature of the oven 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, preferably 1 to 3.5 g / m 2.

The adhesive layer is composed of 4,4'-MDI, 2 (B) contained in a total of 100% by mass of the polyisocyanate component (A) and the polyol component (B) as described above and the specific polyisocyanate component , 4'-MDI and TDI in a total amount of 10 to 34% by mass. The cured product of the adhesive composition is obtained by the following method.

That is, an adhesive composition is coated on the ink layer or a second substrate having an oxygen transmission rate of 100 cc / (m 2 · day · atm) or less at 25 ° C. to form a precursor of the adhesive layer. The amount of the adhesive composition to be applied is appropriately selected depending on the type of the second substrate and the coating conditions, but is usually 1 to 5 g / m 2, preferably 1.5 to 4.5 g / m 2.

Thereafter, a second base material having an oxygen permeability of 100 cc / (m 2 · day · atm) or less is laminated on the precursor of the adhesive layer at 25 ° C., or the ink layer, that is, the white ink layer The surface on which the first base material is not in contact is overlapped, and aging is performed at room temperature or under heating to cure the precursor to form an adhesive layer, thereby producing a laminate. In the case of the adhesive composition of the present embodiment, the time required for aging is about one day. Further, in the case of the adhesive composition of the present embodiment, sufficient adhesion performance can be exhibited even when the environmental humidity is high during coating to aging.

(Second description)

The oxygen permeability of the second substrate used is not more than 100 cc / (m 2 · day · atm) at 25 ° C. The oxygen permeability is affected by the thickness. In the present invention, the second base material may have an oxygen permeability of 100 cc / (m 2 · day · atm) or less from the oxygen permeability per unit thickness (1 μm) (hereinafter referred to as oxygen permeability coefficient) and thickness. The oxygen permeability and the oxygen permeability coefficient are values at 25 캜 unless otherwise stated.

For example, an ethylene-vinyl alcohol copolymer having an ethylene content of 56% has an oxygen transmission coefficient of 3 cc / (m 2 · day · atm), so that it can be used at 1 μm.

On the other hand, a plastic film having a large oxygen permeation coefficient as shown below may also be used depending on the film thickness. That is, the acrylonitrile copolymer having an acrylonitrile content of 70% has an oxygen permeability coefficient of 300 cc / (m 2 · day · atm).

Similarly, when the vinylidene chloride copolymer having an oxygen permeability coefficient of 400 cc / (m 2 · day · atm) has a film thickness of 4 μm or more, the nylon 6 having an oxygen permeability coefficient of 1700 cc / (m 2 · day · atm) , The nylon 66 having an oxygen permeability coefficient of 1925 cc / (m 2 · day · atm) had a film thickness of 19.25 μm or more. The polyethylene terephthalate having an oxygen permeability coefficient of 768 cc / (m 2 · day · atm) The terephthalic acid-bisphenol copolymer polyarylate having an oxygen permeability coefficient of 2580 cc / (m 2 · day · atm) has a film thickness of 25.8 μm or more and a polyacetal having an oxygen permeability coefficient of 4850 cc / (m 2 · day · atm) The polytetrafluoroethylene having an oxygen permeability coefficient of 650 cc / (m 2 · day · atm) has an oxygen permeability coefficient of 1300 cc / (m 2 · day · atm ) Of polyvinylidene fluoride has a film thickness of 13 占 퐉 or more Respectively, can be used as the second substrate.

A vapor deposition film obtained by depositing aluminum, silicon dioxide, aluminum oxide or the like on various plastic films can also be used as the second substrate. In many cases, the thickness of the deposition layer is about 1 to 500 nm, and the influence of the type and thickness of the plastic film on the oxygen permeation becomes extremely small by making such a deposition layer.

For example, an oxygen permeability of 20 to 10 cc / (m 2 · day · atm) and an oxygen permeability of 2 to 0.3 cc / (m 2 · day · atm) for the polyethylene terephthalate film M 2 · day · atm), the oxygen permeability of the polyethylene terephthalate film was 4 to 0.5 cc / (m 2 · day · atm), and the polyethylene terephthalate film had the oxygen permeability of 5 to 0.3 cc / (m &lt; 2 &gt; · day · atm), respectively, and are used as the second substrate.

The metal foil, such as stainless steel, iron, copper or lead, has an oxygen permeability of 0 cc / (m 2 · day · atm) regardless of its thickness.

 As the second substrate, it is preferable to provide a vapor deposition layer on various plastic films or a metal foil. Especially, it is preferable that a metal is vapor-deposited on various plastic films (hereinafter also referred to as vapor deposition film). The metal vapor deposition layer is preferably in contact with the adhesive layer. In a more preferred form, there is an embodiment in which a transparent film and a metal deposition layer are laminated on one main surface of the transparent film in a preferable shape of the second substrate.

The oxygen permeability can be obtained by the method of JIS K7126 using an oxygen permeability measuring apparatus. For example, the oxygen permeability measuring device (О X-TRAN2 / 21) manufactured by Hitachi High-Tech Science Co., Ltd. is equipped with a chromatic sensor which generates a current proportional to the amount of oxygen passing through the sample by carrier gas (nitrogen) Measure the voltage change through the resistor and convert it to oxygen permeability.

[Example]

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to the following examples. All percentages and percentages in the examples are by mass unless otherwise indicated.

&Lt; Measurement method of 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 by GPC (gel permeation chromatography) "Shodex GPC System-21" manufactured by Showa Denko KK. GPC is liquid chromatography in which a substance dissolved in a solvent is separated and quantified by the difference in the molecular size thereof. The solvent is tetrahydrofuran, and the molecular weight is determined in terms of polystyrene.

&Lt; Method of measuring hydroxyl value >

Approximately 1 g of the sample was precisely weighed in a stoppered Erlenmeyer flask and dissolved in 100 mL of a toluene / ethanol (toluene / ethanol = 2/1) mixture. Exactly 5 mL of an acetylating agent (solution of 25 g of acetic anhydride dissolved in pyridine and having a volume of 100 mL) was added and stirred for about 1 hour. Here, the phenolphthalein reagent is added as an indicator and maintained for 30 seconds. Thereafter, the solution was titrated with a 0.1N alcoholic potassium hydroxide solution until it became pale red.

The hydroxyl value was obtained by the following equation (1). The hydroxyl value was a numerical value of the dry state of the resin (unit: mgKOH / g).

(MgKOH / g) = {(b-a) x F x 28.25} / S] / (non-volatile matter concentration / 100) + D

S: Weight of sample (g)

a: consumption of 0.1N alcoholic potassium hydroxide solution (mL)

b: Experiments Consumption of 0.1N Alcoholic Potassium Hydroxide Solution (mL)

F: Potency of 0.1N Alcoholic Potassium Hydroxide Solution

D: acid value (mgKOH / g)

<Acid value measurement method>

Approximately 1 g of the sample was precisely weighed in a stoppered Erlenmeyer flask and dissolved in 100 mL of a mixture of toluene / ethanol (volume ratio: toluene / ethanol = 2/1). The phenolphthalein reagent was added thereto as an indicator and kept together for 30 seconds. The solution was titrated with a 0.1N alcoholic potassium hydroxide solution until the solution became pale red.

The acid value was obtained by the following formula (2). The acid value is a numerical value of the dry state of the resin (unit: mgKOH / g).

(MgKOH / g) = {(5.611 x a x F) / S} / (nonvolatile concentration / 100).

S: Weight of sample (g)

a: consumption of 0.1N alcoholic potassium hydroxide solution (mL)

F: Potency of 0.1N Alcoholic Potassium Hydroxide Solution

&Lt; Method of measuring NCO group content (mass%) >

Approximately 1 g of the sample was precisely measured in a 200 mL Erlenmeyer flask, and 10 mL of 0.5 N di-n-butylamine (toluene solution) and 10 mL of toluene were added and dissolved. The phenolphthalein reagent was added thereto as an indicator and kept for 30 seconds. The solution was titrated with a 0.25N hydrochloric acid solution until it became pale red.

The NCO (mass%) was obtained by the following formula (3).

(Formula 3) NCO group content (mass%) = {(b-a) x 4.202 x F x 0.25} / S

S: Weight of sample (g)

a: consumption of 0.25N hydrochloric acid solution (mL)

b: Experiments Consumed amount of 0.25N hydrochloric acid solution (mL)

F: Potency of 0.25N hydrochloric acid solution

(Synthesis of polyurethane polyurea resin for ink composition)

[Synthesis Example 1-1]

A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet tube was charged with 100 parts by weight of a polyester polyol A1 (copolymer of Kuraraypolyol P-2010, 3-methyl-1,5 pentanediol and adipic acid, 11.17 parts of polyether polyol B1 (EXCENOL2020, polymer of propylene oxide, number average molecular weight 2000, manufactured by Asahi Glass Co., Ltd.), 5.34 parts of isophorone diisocyanate (hereinafter abbreviated as IPDI), 4.36 parts of ethyl acetate, And 0.003 part of 2-ethylhexanoate were placed in the flask and reacted at 90 DEG C for 5 hours under a nitrogen stream, and 7.5 parts of ethyl acetate was added and cooled to obtain a urethane prepolymer solution having an isocyanate group at the terminal.

1.97 parts of isophorone diamine (hereinafter abbreviated to IPDA), 0.2 parts of 2-hydroxyethylethylenediamine, 0.33 part of di-n-butylamine, 30.13 parts of ethyl acetate and 28 parts of isopropyl alcohol (hereinafter abbreviated as IPA) The resulting urethane prepolymer solution was slowly added at room temperature, and then reacted at 50 ° C for 1 hour to obtain a polyurethane polyurea resin solution (PU1) having a solid content of 30% and a weight average molecular weight of 15000.

In this synthesis, the obtained urethane prepolymer solution was dropped to amines and the chain extension reaction was carried out.

[Synthesis Example 1-2]

A polyurethane polyurea resin solution (PU2) was obtained in a similar manner to Synthesis Example 1-1 at the charging ratio shown in Table 1.

[Synthesis Example 1-3]

A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet tube was charged with 11.21 parts of polyester polyol A1, 11.21 parts of polyether polyol B1, 5.36 parts of IPDI, 4.36 parts of ethyl acetate, And the mixture was reacted at 90 占 폚 for 5 hours under a nitrogen stream, to obtain a urethane prepolymer solution having an isocyanate group at the end which was cooled by adding 7.5 parts of ethyl acetate.

Next, 1.87 parts of IPDA, 0.2 parts of di-n-butylamine 0.2 parts of 2-hydroxyethylethylenediamine, and 30.13 parts of ethyl acetate and 28 parts of IPA were added to the resulting urethane prepolymer solution at room temperature. Then, the reaction was conducted at 50 占 폚 for 1 hour to obtain a polyurethane polyurea resin solution (PU3) having a solid content of 30% and a weight average molecular weight of 50,000.

In this Synthesis Example, the urethane prepolymer solution obtained was subjected to a chain extension reaction by dropping an amine.

[Synthesis Examples 1-4 to 1-8]

Polyurethane polyurea resin solutions (PU 4-8) were obtained in a similar manner to Synthesis Example 1-1 at the charging ratios shown in Table 1.

The polyester polyol A2 and the polyether polyol B2 are as follows.

Polyester polyol A2: Clarate polyol P-5010 3-Methyl-1,5-pentanediol copolymer with 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 and Asahi Glass Co., Ltd.

[Synthesis Examples 1-9 to 1-13]

Polyurethane polyurea resin solutions (PU 9 to 13) were obtained in a similar manner to Synthesis Example 1-1 at the charging ratios shown in Table 2.

[Table 1]

[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 (Solvine TA5R, ethyl acetate solution of Nisshin Chemical Industry Co., Ltd., solid content 30% by mass), titanium dioxide (TITONER45M, And 10 parts of an ethyl acetate / IPA mixed solvent (75/25 by mass) were mixed with stirring and kneaded in a sand mill. Then, 32.5 parts of a polyurethane polyurea resin solution (PU1), 30 parts of a vinyl chloride- And 10 parts of an ethyl acetate / IPA mixed solution (mass ratio 75/25) were further added, and the mixture was stirred and then diluted with a mixed solvent of methyl ethyl ketone, normal propyl acetate and IPA (mass ratio 40:40:20) # 3 (untreated) to 15 seconds to obtain an ink composition (i-1).

[Production Examples 2 to 22]

The ink compositions (i-2 to i-22) were obtained in the same manner as in Production Example 1-1 at the charging ratios shown in Tables 3 and 4. CI Pigment Yellow 83 was used as a yellow pigment in addition to titanium dioxide as a pigment.

Further, as the resin other than the polyurethane polyurea resin solution and the vinyl chloride-vinyl acetate copolymer solution C1, all of the following resins were used as a resin solution diluted with ethyl acetate to a solid content of 30% by mass.

Vinyl chloride-vinyl acetate copolymer solution C2 (Solvine CL, manufactured by Nisshin Chemical Industry Co., Ltd.)

Vinyl chloride-vinyl acetate copolymer solution C3 (Solvain AL, manufactured by Nisshin Chemical Industry Co., Ltd.)

Quality screen solution (DLX5-8, manufactured by Nobel Enterprises)

[Table 3]

[Table 4]

Synthesis of polyisocyanate component (A) for adhesive composition

(Synthesis Example 101)

400 parts of polypropylene glycol (hereinafter PPG-400) having a number average molecular weight of about 400, 400 parts of polypropylene glycol having a number average molecular weight of about 2000 (hereinafter referred to as PPG-2000), 400 parts of glycerin with polypropylene glycol 200 parts of triol (hereinafter referred to as PPG-400-3 function), 400 parts of 4,4'-MDI and 600 parts of 2,4'-MDI were placed in a reaction vessel. Then, the mixture was heated at 70 ° C to 80 ° C for 3 hours while being mixed in a nitrogen gas stream to carry out a urethanization reaction to obtain a polyether polyurethane polyisocyanate resin having an isocyanate component content of 14.4% and an MDI monomer content of 33% and an isocyanate group. Hereinafter, this resin is referred to as polyisocyanate A1- (1).

(Synthesis Examples 102-103)

Polyisocyanates A1- (2) and A1- (3), which are polyether polyurethane polyisocyanate resins, were obtained in the same manner as in Synthesis Example 1, according to the compositions shown in Table 5.

(Synthesis Example 104)

80 parts of isophthalic acid, 460 parts of adipic acid, 60 parts of 1,6-hexanediol and 400 parts of diethylene glycol were placed in a reaction vessel and heated to 150 to 240 캜 under stirring in a nitrogen gas stream to carry out an esterification reaction . When the acid value became 1.3 (mgKOH / g), the reaction temperature was set to 200 ° C and the inside of the reaction vessel was gradually decompressed and reacted at 1.3 kPa or less for 30 minutes to give an acid value of 0.4 (mgKOH / g), a hydroxyl value of 80 (mgKOH / g) A polyester polyol 1 having a hydroxyl group at two terminals with a number average molecular weight of about 1,400 was obtained.

150 parts of the obtained polyester resin, 190 parts of PPG-400, 310 parts of 4,4'-MDI and 350 parts of 2,4'-MDI were placed in a reaction vessel and stirred at 70 ° C to 80 ° C For 3 hours to obtain a polyether polyurethane polyisocyanate resin having an isocyanate group content of 17% and an MDI monomer content of 48% and an isocyanate group. Hereinafter, this resin is referred to as polyisocyanate A1- (4).

(Synthesis Example 105)

 200 parts of PPG-400, 200 parts of castor oil, and 145 parts of TDI were placed in a reaction vessel and heated at 80 ° C for 1 hour while being mixed in a nitrogen gas stream to carry out urethanization reaction. 4,4'-MDI: , And 192 parts of 2,4'-MDI were added and heated at 80 DEG C for 3 hours while being mixed in a nitrogen gas stream to carry out a urethanization reaction. The content of isocyanate component was 16.1%, the content of MDI monomer and TDI monomer was 37% Group-containing polyether polyurethane polyisocyanate resin. Hereinafter, this resin is referred to as polyisocyanate A1- (5).

(Synthesis Example 106)

208 parts of adipic acid and 192 parts of diethylene glycol were put into a reaction vessel and heated to 150 to 240 캜 under mixing in a nitrogen gas stream to effect an esterification reaction. When the acid value became 1.3 (mgKOH / g), the reaction temperature was set to 200 ° C and the inside of the reaction vessel was gradually decompressed to react for 30 minutes at 1.3 kPa or lower. The acid value was 0.5 (mgKOH / g), the hydroxyl value was 56.1 A polyester polyol 2 having a hydroxyl group at two terminals of an average molecular weight of about 2000 was obtained.

70 parts of the obtained polyester resin, 367 parts of PPG-400 and 265 parts of TDI were put into a reaction vessel and heated at 80 ° C for 1 hour while being mixed in a nitrogen gas stream to carry out an urethanization reaction. Then, 4,4'-MDI 286 And heated at 80 DEG C for 3 hours while mixing in a nitrogen gas stream to obtain a polyether polyurethane polyisocyanate resin having an isocyanate content of 12%, an MDI monomer and a TDI monomer content of 27%, and an isocyanate group . Hereinafter, this resin is referred to as polyisocyanate A1- (6).

(Synthesis Example 107)

 300 parts of PPG-400, 200 parts of PPG-2000, 480 parts of 4,4'-MDI and 320 parts of 2,4'-MDI were placed in a reaction vessel and heated at 80 ° C for 3 hours while mixing in a nitrogen gas stream To obtain a polyether polyurethane polyisocyanate resin having an isocyanate component content of 15.4% and an MDI monomer content of 34% and an isocyanate group. Hereinafter, this resin is referred to as polyisocyanate A1- (7).

(Synthesis Example 108)

300 parts of PPG-400, 400 parts of PPG-2000, 200 parts of PPG-400-3 and 1000 parts of 4,4'-MDI were put in a reaction vessel and stirred at 80 ° C for 3 hours The urethane reaction was carried out by heating to obtain a polyether polyurethane polyisocyanate resin having an isocyanate group content of 14.4% and an MDI monomer content of 33% and an isocyanate group. Hereinafter, this resin is referred to as polyisocyanate A1- (8).

(Synthesis Example 109)

607 g of xylene diisocyanate (hereinafter referred to as XDI), 672 g of butylene adipate having a molecular weight of about 1000 showing crystallinity at room temperature (Takeake U-2410 manufactured by Takeda Chemical Industries, Ltd.), 118 g of diethylene glycol, 156 g of trifunctional polypropylene glycol (Actcall 32-160, manufactured by Takeda Chemical Industries, Ltd., hereinafter also referred to as PPG-1000 trifunctional) and 0.6 g of benzoyl chloride were put into a reactor, and the mixture was subjected to urethanization reaction at 70 to 80 캜 And 389 g of a polyisocyanate (Takenate D-170HN, hereinafter also referred to as HDI 3 co-polymer), which is a modification of a multimer of an aliphatic polyisocyanate, was added, and uniformly mixed at 70 to 80 ° C under a nitrogen stream To obtain a polyisocyanate component having an isocyanate component content of 6.3%, an XDI monomer (NCO monomer) content of 13%, and an MDI monomer content of 0%. Hereinafter, this resin is referred to as polyisocyanate A1- (9).

[Table 5]

Synthesis of polyol component (B) for adhesive composition

(Synthesis Example 201)

, 115 parts of isophthalic acid (hereinafter referred to as IPA), 304 parts of adipic acid (hereinafter referred to as ADA), 305 parts of diethylene glycol (hereinafter referred to as DEG) and 75 parts of neopentyl glycol (hereinafter referred to as NPG) And the mixture was heated in a temperature range of 150 ° C to 240 ° C while stirring in a nitrogen gas stream to carry out an esterification reaction. When the acid value became 1.3 (mgKOH / g), the reaction temperature was lowered to 200 ° C and the inside of the reaction vessel was gradually decompressed and reacted at 1.3 kPa or less for 30 minutes to obtain an acid value of 0.4 (mgKOH / g), a hydroxyl value of 137 A polyester diol resin having a hydroxyl group at two terminals with an average molecular weight of about 800 was obtained. Hereinafter, this polyol is referred to as polyester diol (b1) -1.

(Synthesis Examples 202 to 207)

Polyether diols (b1) -2 to (b1) -7 were obtained in the same manner as in Synthesis Example 201, according to the compositions shown in Table 6.

(Formulation Example 301)

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

(Formulation examples 302 to 317)

Polyol components B- (2) to B- (10) were obtained in the same manner as in Formulation Example 301, according to the compositions shown in Table 7.

[Table 6]

[Table 7]

(Preparation Example 401)

100 parts of polyisocyanate component A1- (1) obtained in Synthesis Example 101 and 50 parts of polyol component B- (1) obtained in Formulation Example 301 were mixed at 60 占 폚 to obtain a solventless adhesive composition AD1. In addition, the adhesive composition AD1 for durability contains 182 moles of an isocyanate group derived from the polyisocyanate component A1- (1) in 100 moles of the hydroxyl group in the polyol component.

The amount of isocyanate component relative to 100 moles of hydroxyl groups is determined as follows.

Amount of isocyanate group relative to 100 moles of hydroxyl group = [isocyanate group (eq.) / Hydroxyl group (eq.) X 100

Isocyanate group (eq.) = NCO content (mass%) / (42 x 100)

Hydroxyl group (eq.) = Hydroxyl group / 56100

The total content of 4,4'-MDI, 2,4'-MDI, 2,2'-MDI and TDI (hereinafter referred to as isocyanate monomer) contained in 100% of the solventless adhesive composition was 22%. The content of isocyanate monomer was determined by measuring the total area of the peak areas derived from the MDI monomers at Mn = 200 to 300 and the peak areas derived from the TDI monomer at Mn = 100 to 200 observed on the GPC chart as the total peaks observed on the GPC chart . &Lt; / RTI &gt;

 Isocyanate monomer content (%) = (sum of the maximum areas of the isocyanate monomers / total area of all the heights) x 100

(Production Examples 402 to 416)

 According to the composition shown in Table 8, the adhesive composition AD2-AD16 was obtained in the same manner as in Production Example 401.

[Table 8]

[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 were subjected to a corona-treated PET film (Toyobo Ester # E5100 #) which was a first substrate at a printing speed of 50 m / min by a gravure printing machine equipped with a gravure plate 12) and dried or cured by passing through an oven at 60 DEG C to form an ink layer on the PET film.

[Production of laminate]

On the surface of the ink layer printed on the PET film using a solventless test coater, the solventless adhesive composition AD1 obtained in Production Example 401 was applied at a coating rate of 200 m / min at a temperature of 60 ° C (coating amount: 2 g / m 2) (VMCPP, thickness: 25 mu m) having an oxygen permeability of 20 cc / (m 2 · day · atm) was laminated to obtain a laminate in a preparation step (pre-laminate).

 These free (preliminary) laminate were aged for one day under an environment of 25 ° C and 80% RH, and the adhesive layer was cured to prepare a laminate. With respect to the obtained laminate, the adhesion of the laminate and the surface state of the laminate were evaluated by the following methods. The results are shown in Table 9.

(Adhesive force)

The laminate was cut into a length of 300 mm and a width of 15 mm to prepare a test piece. The T-type peel strength (N) between PET / VMCPP was measured with an Instron type tensile tester at a peeling speed of 300 mm / min under an environment of 25 캜 at a width of 15 mm. This test was repeated five times, and the average value thereof was determined and evaluated according to the following criteria.

5: Adhesive strength 1.5N or more

4: Adhesive strength of 1.0 N or more and less than 1.5 N

3: Adhesive strength of 0.6 N or more and less than 1.0 N

2: Adhesive strength of 0.3 N or more and less than 0.6 N

1: Adhesion less than 0.3N

(Surface state of the laminate)

The evaporated portion was visually observed through the ink layer and the adhesive layer on the first substrate side and evaluated according to the following criteria.

5: No peel-like patterns and small spots are observed in the deposition area.

4: Small spots are not observed in the deposition area, but pattern of citron skin pattern is slightly observed. No problem in use.

3: Small spots are not observed in the deposition area, but many patterns of citrus skin are observed. No problem in use.

2: Not only the appearance of citron skin but also a small speck pattern is observed on the deposition surface.

1: Not only the appearance of citron skin but also the pattern of small spots are observed on the deposition surface.

[Table 9]

As shown in Table 9, Examples 1 to 13, in which an ink layer was formed with the ink composition of this Example, exhibited excellent appearance and adhesion after aging at 25 캜. On the other hand, in Comparative Example 1, the molecular weight of the polyurethane polyurea resin was low, the cohesive force of the ink layer was insufficient, and the bonding strength was particularly poor. In Comparative Example 2, since the molecular weight of the polyurethane polyurea resin is high and a uniform ink layer can not be formed, the appearance of the laminate is deteriorated. In Comparative Example 3, the ratio of the polyester polyol in the high molecular weight polyol having a number average molecular weight of 400 to 5000 in the polyurethane polyurea resin was low, so that the isocyanate monomer in the adhesive composition tends to penetrate into the ink layer and the adhesion and the appearance of the laminate deteriorate. The appearance of the laminate is poor. In Comparative Example 4, the total concentration of the urethane bond and the urea bond in the polyurethane polyurea resin is low, so that the isocyanate monomer in the adhesive composition tends to penetrate into the ink layer, and the adhesive strength and appearance of the laminate deteriorate. In Comparative Example 5, since the total concentration of the urethane bond and urea bond of the polyurethane polyurea resin in the ink layer is higher than 2.4 mmol / g, a uniform ink layer can not be formed and the appearance of the laminate deteriorates. Further, since the adhesion of the ink layer to the transparent substrate tends to be lowered, the adhesive force is also low. In Comparative Examples 6 and 7, no vinyl chloride-vinyl acetate copolymer was contained in the ink composition, and in Comparative Example 8, a ratio of 5% or less of 100% by mass of the sum of the polyurethane polyurea resin and the vinyl chloride- Vinyl chloride-vinyl acetate copolymer. In Comparative Examples 6 to 8, since the chemical resistance derived from the vinyl chloride-vinyl acetate copolymer in the ink layer was significantly lowered, the isocyanate monomer in the adhesive composition penetrated into the ink layer as in Comparative Examples 3 and 4, Adhesion is reduced. In Comparative Example 9, the vinyl chloride-vinyl acetate copolymer content exceeded the range of 5 to 40%, so the adhesion of the ink layer to the transparent substrate was poor and the adhesion was particularly bad.

[Examples 14 to 24], [Comparative Examples 10 to 13]

The procedure of Example 1 was repeated, except that i-2 was used in place of the ink composition i-1 and the solventless adhesive compositions AD2 to AD16 obtained in Production Examples 402 to 416 were used instead of the adhesive composition AD1 as shown in Table 10, We got sieve, and it was likewise evaluated. The results are shown in Table 10.

[Table 10]

As shown in Table 10, Examples 14 to 24, in which an adhesive layer was formed of the adhesive composition of this Example, exhibited excellent appearance and adhesive force after aging at 25 ° C. In contrast, Comparative Example 10 uses the urethane prepolymer (a) obtained by using only 4,4'-MDI as the isocyanate component (A) and the isocyanate component A1- (8) containing 4,4'-MDI, Is too fast, the leveling property of the adhesive layer is lowered during curing, so that the appearance is not sufficient. In Comparative Example 11, since the polyester polyol B- (9) having a weight average molecular weight of 4000 was used as the polyol component (B), the reactivity with the isocyanate component (A) after coating was lowered and the 4,4'- , The ink film is broken due to penetration of the isocyanate monomer, and thus the appearance is poor. In Comparative Example 12, since the polyester polyol B- (10) having a mass average molecular weight of 300 was used as the polyol component (B), the reaction rate with the isocyanate component (A) was too fast and the leveling property of the adhesive layer The appearance is not enough. In Comparative Example 13, the isocyanate component (A) used is an isocyanate component A1- (9) derived from XDI and HDI, and since the curing rate is slow, the strength is not sufficient after aging at 25 ° C.

[Examples 25 to 36], [Comparative Examples 14 to 22]

As shown in Table 11, a laminate was obtained in the same manner as in Example 1, except that the adhesive composition AD1 obtained in Production Example 410 was used instead of the adhesive composition AD1. The results are shown in Table 11.

[Table 11]

It can be seen from Table 11 that even if the adhesive composition is changed, the trend is similar to that of Table 9.

[Industrial Availability]

The laminate according to the present invention can be applied to the entire laminate having an ink layer. It is particularly useful for packaging materials such as foods, clothes, cosmetics and the like.

 This application claims priority based on Japanese Patent Application No. 2016-66284, filed on March 29, 2016, and Japanese Patent Application No. 2016-155231, filed August 8, 2016, .

Claims (5)

An ink layer, an adhesive layer, and a second substrate having an oxygen transmission rate of at least 100 cc / (m 2 · day, atm) at 25 ° C in this order,
When the ink layer meets all the conditions (1) to (5) below
Wherein the adhesive layer satisfies 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) 5 to 40% by mass of the vinyl chloride-vinyl acetate copolymer in a total of 100% by mass of the polyurethane polyurea resin and the vinyl chloride-vinyl acetate copolymer.
(3) The polyurethane polyurea resin,
A polyurethane block having a structural unit derived from a high molecular weight polyol having a number average molecular weight of 400 to 5000 and a structural unit derived from a polyisocyanate compound and
Having a chain extending unit derived from a compound having an amino group
The chain extending unit from above the polyurethane block is bonded by a urea bond
Wherein the polyester polyol is contained in an amount of 5% by mass or more in 100% by mass of the polymer polyol having a number average molecular weight of 400 to 5,000.
(4) The polyurethane polyurea resin has a mass average molecular weight of 15,000 to 70,000.
(5) The total concentration of urethane bond and urea bond 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)
A urethane prepolymer (a) having an isocyanate group and 4,4'-diphenylmethane diisocyanate,
And at least one isocyanate selected from the group consisting of 2,4'-diphenylmethane diisocyanate and trilene diisocyanate.
(13) The process for producing a urethane prepolymer as described in any one of (1) to (10), wherein the isocyanate group-containing urethane prepolymer (a) comprises 4,4'-diphenylmethane diisocyanate A reaction product of an isocyanate component further containing one kind of component and a polyol in which a polyether polyol is essential,
or,
A reaction product of 4,4'-diphenylmethane diisocyanate and a polyol, and a reaction product of at least one isocyanate component selected from the group consisting of 2,4'-diphenylmethane diisocyanate and triethylene diisocyanate and a polyol, Wherein at least one of the polyols is a polyether polyol.
(14) The polyol component (B) essentially contains a polyester polyol having a number average molecular weight of 500 to 3000.
(15) The total amount of 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate and styrene diisocyanate contained in 100% by mass of the adhesive composition is 10 to 34% by mass. The laminate according to claim 1, wherein the pigment contained in the ink layer is titanium dioxide.  The method according to claim 1 or 2, wherein the second substrate comprises a transparent film and a metal deposition layer laminated on one main surface of the transparent film, wherein the metal deposition layer is in contact with the adhesive layer, sieve. An ink layer, an adhesive layer, and a second substrate having an oxygen transmission rate of 100 cc / (m 2 · day · atm) or less at 25 ° C are laminated in this order on the first substrate, A process for producing a laminate, comprising the steps of (I) to (VI)
(I-1) a reaction product of a high molecular weight polyol having a number average molecular weight of 400 to 5000, a polyisocyanate compound and a compound having an amino group, wherein the polyester polyol is a reaction product of 100% by mass of the high molecular weight polyol having a number- By mass or more and a total concentration of urethane bond and urea bond contained in 1 g of polyurethane polyurea resin is 1.3 to 2.4 mmol / g and a number average molecular weight is 15,000 to 70,000.
(I-2) A polyurethane resin composition comprising the polyurethane polyurea resin, a vinyl chloride-vinyl acetate copolymer, a pigment and an organic solvent, the polyurea polyurea resin and the vinyl chloride-vinyl acetate copolymer in a total amount of 100% And 5 to 40 mass% of a vinyl-vinyl acetate copolymer.
(II-1) a urethane prepolymer (a) having an isocyanate group, and 4,4'-diphenylmethane diisocyanate, and is selected from the group consisting of 2,4'-diphenylmethane diisocyanate and trilene diisocyanate A process for preparing a polyisocyanate component (A) further comprising at least one isocyanate component,
The urethane prepolymer (a)
An isocyanate component containing 4,4'-diphenylmethane diisocyanate as essential components and further containing at least one member selected from the group consisting of 2,4'-diphenylmethane diisocyanate and trilene diisocyanate, and a polyether polyol The required polyol may be reacted with excess isocyanate groups,
or,
Wherein at least one kind of isocyanate component selected from the group consisting of 2,4'-diphenylmethane diisocyanate and trilene diisocyanate and a polyol having essential polyether polyol as essential components, wherein 4,4'-diphenylmethane diisocyanate is essential, Is reacted with an excess of isocyanate group, respectively, and then mixed.
(II-2) The polyisocyanate component (A) and the polyol component (B) essentially containing a polyester polyol having a number average molecular weight of 500 to 3000 are mixed,
The total amount of 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate and trilene diisocyanate contained in the total of 100 mass% of the polyisocyanate component (A) and the polyol component (B) And 10 to 34% by mass of the adhesive composition.
(III) A step of coating the ink composition on the first substrate and drying or curing the ink composition to obtain the ink layer.
(IV) A step of coating the adhesive composition on the ink layer to form a precursor of the adhesive layer.
(V) a step of overlapping the second substrate on the precursor of the adhesive layer.
(VI) a step of curing the precursor of the adhesive layer after the step (V) to form the adhesive layer. An ink layer, an adhesive layer and a second substrate having an oxygen transmission rate of 100 cc / (m 2 · day · atm) or less at 25 ° C are laminated in this order on the first substrate, A process for producing a laminate, which comprises the steps of (I) to (III), (VII) to (IX)
(I-1) a reaction product of a high molecular weight polyol having a number average molecular weight of 400 to 5000, a polyisocyanate compound and a compound having an amino group, wherein the polyester polyol is a reaction product of 100% by mass of the high molecular weight polyol having a number- By mass or more and a total concentration of urethane bond and urea bond contained in 1 g of polyurethane polyurea resin is 1.3 to 2.4 mmol / g and a number average molecular weight is 15,000 to 70,000.
(I-2) A polyurethane resin composition comprising the polyurethane polyurea resin, a vinyl chloride-vinyl acetate copolymer, a pigment and an organic solvent, the polyurea polyurea resin and the vinyl chloride-vinyl acetate copolymer in a total amount of 100% And 5 to 40 mass% of a vinyl-vinyl acetate copolymer.
(II-1) a urethane prepolymer (a) having an isocyanate group, and 4,4'-diphenylmethane diisocyanate, and is selected from the group consisting of 2,4'-diphenylmethane diisocyanate and trilene diisocyanate A process for preparing a polyisocyanate component (A) further comprising at least one isocyanate component,
The urethane prepolymer (a)
An isocyanate component containing 4,4'-diphenylmethane diisocyanate as essential components and further containing at least one member selected from the group consisting of 2,4'-diphenylmethane diisocyanate and trilene diisocyanate, and a polyether polyol The required polyol may be reacted with excess isocyanate groups,
or,
Wherein at least one kind of isocyanate component selected from the group consisting of 2,4'-diphenylmethane diisocyanate and trilene diisocyanate and a polyol having essential polyether polyol as essential components, wherein 4,4'-diphenylmethane diisocyanate is essential, Is reacted with an excess of isocyanate group, respectively, and then mixed.
(II-2) The polyisocyanate component (A) and the polyol component (B) essentially containing a polyester polyol having a number average molecular weight of 500 to 3000 are mixed,
The total amount of 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate and trilene diisocyanate contained in the total of 100 mass% of the polyisocyanate component (A) and the polyol component (B) And 10 to 34% by mass of the adhesive composition.
(III) A step of coating the ink composition on the first substrate and drying or curing the ink composition to obtain the ink layer.
(VII) A step of coating the adhesive composition on the second base material to form a precursor of the adhesive layer.
(VIII) A step of overlapping the ink layer on the precursor of the adhesive layer.
(IX) A step of curing the precursor of the adhesive layer to form the adhesive layer after the step (VIII).