JP2017136817A - Laminate and production method of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate having a good appearance of a printed part through process of applying an adhesive at a high speed, for example, at an application speed of 200 m/min and of aging at a low temperature of 40°C or lower in a short time, when a gas barrier base material having a metal vapor deposition layer on a film is used.SOLUTION: The laminate includes a transparent base material 1, a white ink layer, an adhesive layer, and a base material 2, in this order. The white ink layer is a dried or cured product of a white ink containing an amino-based silane coupling agent by 0.15 to 7 mass% in 100 mass% of a solid content of an ink composition. The adhesive layer is a cured product of an adhesive composition comprising a polyisocyanate component (A) and a polyol component (B), in which the polyisocyanate component (A) comprises a urethane prepolymer (a) having an isocyanate group and 4,4'-diphenylmethane diisocyanate and further contains at least one isocyanate selected from the group consisting of 2,4'-diphenylmethane diisocyanate and tolylene diisocyanate.SELECTED DRAWING: None

Description

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

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

In recent years, due to the demand for simple equipment, there has been a strong demand for removal of the adhesive composition from organic solvents, and research into solvent-free has been actively conducted.
For example, Patent Document 1 discloses a solventless laminating adhesive composition containing a polyol component (1) and a polyisocyanate component (2) composed of two types of polyisocyanate compounds.
Further, Patent Document 2 contains a polyol component (1) and a polyisocyanate component (2) essential for a trifunctional polyisocyanate compound, the branching point concentration is in a specific range, and the hydroxyl group mole number: isocyanate group. A solventless laminate adhesive composition having a mole number of 1: 1 to 1: 3 is disclosed.
Patent Document 3 discloses a solvent-free adhesive composition containing a polyol component (A) and an isocyanate component (B) essentially containing isophorone diisocyanate.
Patent Document 4 discloses a solventless adhesive composition containing a polyol component (A), a polyisocyanate compound (B), and a powder (C) having a specific particle size.
Patent Document 5 includes a polyisocyanate component (A) and a polyol component (B), and the polyisocyanate component (A) contains 2,4′-diphenylmethane diisocyanate (a1) and 4,4′-MDI (a2). ) And a polyol essential for the polyether polyol (a3) are reacted under an excess of isocyanate group, and the polyol component (B) has a number average molecular weight of 500 or more and 3000 or less. An adhesive composition containing a polyester diol (b1) as an essential component and further containing at least one of a diol (b2) or a triol (b3) having a number average molecular weight of 50 or more and less than 500 is disclosed.
Further, claim 2 of Patent Document 6 includes a polyethylene terephthalate film layer (F1) for exterior packaging, a dry coating layer (P) for printing ink, a dry coating layer (C) for coating resin, and a solventless adhesive layer (A ), A plastic film laminate having a metal vapor-deposited layer or metal foil (M) and an interior plastic film layer (F2) in this order.
Patent Document 7 discloses a two-component curable solventless adhesive composition containing a specific amount of a crystalline polyol component in the total amount of the polyol component (A) and the polyisocyanate component (B). .
Patent Document 8 discloses an adhesive containing a specific polyisocyanate component (A) containing a urethane prepolymer made from polyether polyol and crude MDI, and a specific polyol component (B) containing polyester diol as an essential component. An agent composition is described.

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

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

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

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

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

In [0013] and [0014] of Patent Document 6, a dry coating layer (P) of printing ink is provided between an outer polyethylene terephthalate film layer (F1) and a dry coating layer (C) of a coating resin. The coating resin constituting the dry film layer (C) of the coating resin is disclosed to improve the appearance of the ink part using a binder for printing ink.
However, the processing speed specifically shown in the examples, that is, the adhesive coating speed is only 10 m / min. And is slow. Since the solvent-free adhesive composition is solvent-free, until now, when the coating speed is increased, the coating surface becomes rough, and thus it has been impossible to achieve both improvement in coating speed and improvement in appearance. From the viewpoint of improving productivity, it is desirable that a solvent-free adhesive composition be a laminate having a good appearance of the ink part at the same level as the solvent-type adhesive composition, for example, at a coating speed of about 200 m / min. It has come to be.

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

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

  An object of the present invention is to use a substrate having excellent gas barrier properties, for example, a substrate having an oxygen permeability of 100 (CC / m 2 · 24 h · atm, at 25 ° C.) or less at a high speed, for example, a coating speed of 200 m / min. The adhesive composition is applied in the above, and a laminate having a good appearance of the printed portion is provided by aging at a low temperature of 40 ° C. or lower and in a short time.

This invention is made | formed in view of the said subject, Comprising: This invention relates to the laminated body which has the transparent base material 1, the specific white ink layer, the specific adhesive bond layer, and the base material 2 in this order. .
That is, the white ink layer constituting the laminate of the present invention satisfies all the following conditions (1) to (3), and the adhesive layer satisfies all the following conditions (11) to (15).
(1) The white ink layer is a dried or cured product of a white ink composition containing a polyurethane polyurea resin, a white inorganic pigment, an amino silane coupling agent, and an organic solvent.
(2) The polyurethane polyurea resin has a hydroxyl group of 0.1 to 20 (mgKOH / g).
(3) 0.15-7 mass% of said amino-type silane coupling agent is contained in 100 mass% of solid content of an ink composition.
(11) The number average molecular weight is a cured product of the adhesive composition containing the polyisocyanate component (A) and the polyol component (B).
(12) The polyisocyanate component (A) includes 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 tolylene diisocyanate. And at least one isocyanate.
(13) The urethane prepolymer (a) having an isocyanate group essentially comprises 4,4′-diphenylmethane diisocyanate, and includes at least one selected from the group consisting of 2,4′-diphenylmethane diisocyanate and tolylene diisocyanate. Furthermore, it is a reaction product of an isocyanate component that contains and a polyol that essentially requires a polyether polyol,
Or
4,4′-diphenylmethane diisocyanate is essential, and is a mixture of at least one isocyanate component from the group consisting of 2,4′-diphenylmethane diisocyanate and tolylene diisocyanate and a reaction product of a polyol, One is a mixture that requires a polyether polyol.
(14) The polyol component (B) contains a polyester polyol having a number average molecular weight of 500 or more and 3000 or less as an essential component.
(15) The total amount of 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate and tolylene diisocyanate contained in 100% by mass of the adhesive composition is 10 to 34% by mass.

In the laminate of the present invention, the amino silane coupling agent contained in the white ink layer has a primary amino group, or has a secondary amino group and four or more alkoxy groups. Is preferred.
Furthermore, in the laminate of the present invention, it is preferable that the silane coupling agent having a primary amino group among the amino silane coupling agents further has a secondary amino group.

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

Furthermore, the present invention includes a transparent substrate 1, a specific white ink layer, a specific adhesive layer, and a substrate 2 having an oxygen permeability of 100 (CC / m ² · 24h · atm · at 25 ° C) or less in this order. It is a manufacturing method of the laminated body which has, Comprising: It is related with the manufacturing method of the laminated body containing following process (I)-(VI).
(I) A polyurethane polyurea resin having a hydroxyl value of 0.1 to 20 (mgKOH / g), a white inorganic pigment, an organic solvent, and 0.15 to 7% by weight of amino in 100% by weight of the solid content of the ink composition A step of preparing a white ink composition containing a silane coupling agent.
(II-1) an isocyanate component essentially comprising 4,4′-diphenylmethane diisocyanate and further comprising at least one selected from the group consisting of 2,4′-diphenylmethane diisocyanate and tolylene diisocyanate, and a polyol essentially comprising a polyether polyol Is reacted under conditions of excess isocyanate groups,
Or
A condition in which 4,4′-diphenylmethane diisocyanate is essential, each of at least one isocyanate component from the group consisting of 2,4′-diphenylmethane diisocyanate and tolylene diisocyanate, and a polyol in which polyether polyol is essential, and an isocyanate group excess condition After reacting below, mix,
A urethane prepolymer (a) having an isocyanate group;
A polyisocyanate component (A) comprising 4,4′-diphenylmethane diisocyanate and further comprising at least one isocyanate selected from the group consisting of 2,4′-diphenylmethane diisocyanate and tolylene diisocyanate;
(II-2) The polyisocyanate component (A) and a polyol component (B) containing a polyester polyol having a number average molecular weight of 500 to 3000 as an essential component are mixed,
The total amount of 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate and tolylene diisocyanate contained in a total of 100 mass% of the polyisocyanate component (A) and the polyol component (B) is 10 to 10%. The process of preparing the adhesive composition which is 34 mass%.
(III) A step of applying the white ink composition to the transparent substrate 1 and drying or curing to obtain a white ink layer.
(IV) A step of applying the adhesive composition on the white ink layer to form a precursor of the adhesive layer.
(V) A step of stacking the base material 2 on the precursor of the adhesive layer.
(VI) A step of curing the precursor of the adhesive layer to form an adhesive layer.

Furthermore, the present invention provides a transparent substrate 1, a specific white ink layer, a specific adhesive layer, and a substrate 2 having an oxygen permeability of 100 (CC / m ² · 24h · atm · at 25 ° C) or less in this order. The present invention relates to another method for manufacturing a laminated body. That is, it is related with the manufacturing method of the laminated body containing following process (I)-(III), (VII)-(IX).
(I) A polyurethane polyurea resin having a hydroxyl value of 0.1 to 20 (mgKOH / g), a white inorganic pigment, an organic solvent, and 0.15 to 7% by weight of amino in 100% by weight of the solid content of the ink composition A step of preparing a white ink composition containing a silane coupling agent.
(II-1) an isocyanate component essentially comprising 4,4′-diphenylmethane diisocyanate and further comprising at least one selected from the group consisting of 2,4′-diphenylmethane diisocyanate and tolylene diisocyanate, and a polyol essentially comprising a polyether polyol Is reacted under conditions of excess isocyanate groups,
Or
A condition in which 4,4′-diphenylmethane diisocyanate is essential, each of at least one isocyanate component from the group consisting of 2,4′-diphenylmethane diisocyanate and tolylene diisocyanate, and a polyol in which polyether polyol is essential, and an isocyanate group excess condition After reacting below, mix,
A urethane prepolymer (a) having an isocyanate group;
A polyisocyanate component (A) comprising 4,4′-diphenylmethane diisocyanate and further comprising at least one isocyanate selected from the group consisting of 2,4′-diphenylmethane diisocyanate and tolylene diisocyanate;
(II-2) The polyisocyanate component (A) and a polyol component (B) containing a polyester polyol having a number average molecular weight of 500 to 3000 as an essential component are mixed,
The total amount of 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate and tolylene diisocyanate contained in a total of 100 mass% of the polyisocyanate component (A) and the polyol component (B) is 10 to 10%. The process of preparing the adhesive composition which is 34 mass%.
(III) A step of applying the white ink composition to the transparent substrate 1 and drying or curing to obtain a white ink layer.
(VII) A step of applying the adhesive composition on the base material 2 to form an adhesive layer precursor.
(VIII) A step of overlaying the white ink layer on the precursor of the adhesive layer.
(IX) A step of curing the adhesive layer precursor to form an adhesive layer.

  According to the present invention, when a base material having an oxygen permeability of 100 (CC / m 2 · 24 h · atm, at 25 ° C.) or less and excellent in gas barrier properties is used, the adhesive composition is formed at a high speed, for example, at a coating speed of 200 m / min. Even if it is applied and aging is performed at a low temperature of 40 ° C. or lower for a short time, an adhesive performance of 0.6 N or more can be developed with a width of 15 mm, and a laminate having a good appearance of the printed portion can be provided.

The white ink layer constituting the laminate of the present invention is formed from a white ink composition (hereinafter also abbreviated as ink composition).
As described above, the ink composition contains a polyurethane polyurea resin, a white inorganic pigment, an amino silane coupling agent, and an organic solvent.
First, the polyurethane polyurea resin contained in the ink composition will be described. The polyurethane polyurea resin in the present invention is a reaction product of a urethane prepolymer having an isocyanate group obtained by reacting a polymer polyol and a polyisocyanate compound and a compound having an amino group.

The polymer polyol referred to in the present invention is a well-known polymer polyol for gravure inks and flexographic inks, and can be obtained by polymerization reaction, condensation reaction, natural product, etc., many of which have an average molecular weight of 400 to 10,000. It is.

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

  Among the polymer polyols, polyester polyols and polyether polyols are preferable from the viewpoint of adhesion of the ink layer to the transparent substrate 1 and solubility in the solvent of the ink composition, and the number average molecular weight is 500 to 5,000. It is preferable. Polyester polyols include diols having one or more branched structures selected from 2-methyl-1,3-propanediol, 2-ethyl-2butyl-1,3-propanediol, 3-methyl-1,5-pentanediol, and the like. Since the polyester polyol obtained by polymerizing adipic acid has a branched structure, it is particularly excellent in adhesion and solubility to the substrate. In particular, a polyester polyol obtained by polymerizing 3-methyl-1,5-pentanediol and adipic acid is preferable. Polyether polyols are preferably propylene oxide polymers having moderate flexibility in terms of adhesion to the substrate. More preferably, a polyester polyol having a branched structure and a polyether polyol are used in combination.

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

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

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

Examples of the chain extender include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, and dicyclohexylmethane-4,4′-diamine. Furthermore, as a chain extender capable of adding a hydroxyl group to the side chain of the polyurethane polyurea resin, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di- Use amines having a hydroxyl group in the molecule such as 2-hydroxyethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypyrroleethylenediamine, di-2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, etc. I can do it. These chain extenders can be used alone or in combination of two or more, but it is preferable to use isophoronediamine and 2-hydroxyethylethylenediamine in combination.

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

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

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

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

The mass average molecular weight of the polyurethane polyurea resin in the present invention is 15000 or more from the viewpoint of blocking resistance of the obtained ink composition, and can appropriately disperse the pigment, and the work in the printing process using the obtained ink composition It is preferably 70000 or less from the viewpoint of good efficiency.

The polyurethane polyurea resin in this invention has a hydroxyl group in the side chain or terminal of a polyurethane polyurea resin, and a hydroxyl value is 0.1-20 mgKOH / g, It is preferable that it is 1-15 mgKOH / g. When the hydroxyl value is 0.1 mgKOH / g or more, a tough ink layer crosslinked with an amino silane coupling agent described later can be obtained. Since the components in the adhesive composition to be described later do not easily penetrate into the tough ink layer, the appearance and physical properties of the laminate are improved. When the hydroxyl value is 20 mgKOH / g or less, the cohesive strength of the polyurethane polyurea resin is increased and the components in the adhesive composition are less likely to penetrate into the ink layer, so that the laminate appearance and physical properties are improved.
Examples of the method for adding a hydroxyl group to the side chain of the polyurethane polyurea resin include using amines having the hydroxyl group as a chain extender. Moreover, the method of adding a hydroxyl group to the terminal of a polyurethane polyurea resin includes using monoamines having the hydroxyl group as a terminal blocking agent. In the polyurethane polyurea resin of the present invention, hydroxyl groups can be added to the polyurethane polyurea resin by any method, but hydroxyl groups are preferably added to both side chains and terminals.

Next, the amino silane coupling agent contained in the ink composition will be described.
The amino-based silane coupling agent in the present invention indicates a compound having a primary to tertiary amino group and an alkoxysilyl group in one molecule. The alkoxysilyl group in the amino silane coupling agent molecule forms a crosslink with the hydroxyl group present on the surface of the polyurethane polyurea resin or white inorganic pigment in the ink composition, so that the laminated adhesive composition penetrates. A dry or cured product of a strong tough ink composition is formed, and the leveling property of the adhesive composition is improved, so that the appearance of the laminate is improved. In addition, since the isocyanate monomer in the adhesive composition or in the precursor of the adhesive layer (hereinafter also referred to as adhesive) does not penetrate into the ink layer, it does not hinder the curing of the adhesive layer and is a good laminate. Physical properties can be realized.

The ink composition in the present invention contains the amino silane coupling agent in an amount of 0.15 to 7% by mass and preferably 0.5 to 3% by mass in 100% by mass of the solid content of the ink composition. . When the amino silane coupling agent content is 0.15% by mass or more, the ink layer can be sufficiently crosslinked, and the laminate appearance and physical properties can be improved.
Moreover, when the amino silane coupling agent content is 7% by mass or less, the appearance and physical properties of the laminate can be improved. The reason for this is considered as follows. The amino silane coupling agent in the ink layer also reacts with the polyisocyanate component (A) in the adhesive, or the basicity during the curing reaction between the polyisocyanate component (A) and the polyol (B) in the adhesive. It can also act as a catalyst. Since the amino group is more reactive with the isocyanate group than the hydroxyl group, the polyisocyanate component (A) is more preferable than the polyol (B) when the excess amino silane coupling agent is contained in the ink layer. Also reacts preferentially with the amino-based silane coupling agent in the ink layer, and the polyisocyanate component (A) in the adhesive layer during curing is insufficiently reacted with the polyol (B), The adhesive strength of the body is inferior. On the other hand, when the curing reaction between the polyisocyanate component (A) and the polyol (B) is promoted by an excess amino silane coupling agent in the ink layer, the viscosity of the adhesive layer in the middle of curing increases. As a result, the adhesive layer in the middle of curing cannot spread evenly with respect to the ink layer and the appearance of the laminate is inferior.

The amino silane coupling agent in the present invention preferably has a primary amino group. By having a primary amino group, the hydrolysis and condensation reactivity of the alkoxy group in the same molecule is superior, and the crosslinked composition is efficiently formed in the ink composition. Penetration can be suppressed, and the appearance of the laminate is improved. Examples of such compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, and 3-aminopropylmethyldiethoxysilane.

  More preferably, the amino-based silane coupling agent having a primary amino group also has a secondary amino group. By having the primary and secondary amino groups, the hydrolysis reactivity and condensation reactivity of the alkoxy group in the same molecule are particularly excellent, and the laminate appearance and laminate physical properties are particularly good. Examples of such compounds include N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and the like.

The amino silane coupling agent in the present invention preferably has a secondary amino group and four or more alkoxy groups. Secondary amino groups tend to have poorer hydrolysis and condensation reactivity of alkoxy groups than primary amino groups, but the presence of four or more alkoxy groups enables efficient cross-linking with one molecule. Since the structure can be formed, the appearance of the laminate is as good as the amino silane coupling agent having a primary amino group. Examples of such compounds include bis (3-trimethoxysilylpropyl) amine, bis (3-
Examples include triethoxysilylpropyl) amine, bis (3-methyldimethoxysilylpropyl) amine, bis (triethoxysilylmethyl) amine, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine, and the like.

  The ink composition in the present invention contains a white inorganic pigment. The white inorganic pigment is preferably contained in an amount sufficient to ensure the density of the printed material, that is, in a proportion of 5 to 50% by mass in the ink composition. Examples of white inorganic pigments include titanium oxide, zinc oxide, barium sulfate, calcium carbonate, aluminum hydroxide, chromium oxide, silica, mica (mica), and the like.

  In particular, the white inorganic pigment is preferably titanium oxide. Since titanium oxide is excellent in chemical resistance, it is possible to suppress penetration of the adhesive composition into the white ink layer, and a laminate having a good appearance can be obtained from the viewpoint of coloring power and hiding power. Moreover, it is suitable for obtaining the laminated body which has a physical property and an external appearance from the point of the bridge | crosslinking effect | action of the titanium oxide surface and the said amino-type silane coupling agent.

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

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

  The ink composition in the present invention can be produced by dissolving and / or dispersing a resin, a pigment or the like in an organic solvent. Specifically, a pigment dispersion is produced by dispersing a white inorganic pigment in a polyurethane polyurea resin and other resins, and if necessary, other compounds in an organic solvent, and the resulting pigment dispersion is polyurethane polyurea. An ink composition can be produced by blending resin, other resins, organic solvents, and other compounds as required. The process for obtaining the pigment dispersion is also referred to as a kneading process.

The method for adding an amino silane coupling agent to the ink composition may be a general method for adding an additive to the ink composition, and is not particularly limited. For example, (
1) Amino silane coupling agent is treated in advance by dry or wet process on the pigment. (2) Amino silane coupling agent is added all at once when the pigment is kneaded. There are methods such as adding a silane coupling agent, (4) adding to the ink immediately before printing.

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

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

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

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

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

The polyisocyanate component (A) includes a urethane prepolymer (a) having an isocyanate group and 4,4′-MDI, and further includes at least one isocyanate selected from the group consisting of 2,4′-MDI and TDI. .
The urethane prepolymer (a) can be obtained by reacting an isocyanate component and a polyol under an excess of isocyanate groups,
Is a reaction product of an isocyanate component containing 4,4′-MDI as an essential component and containing at least one selected from the group consisting of 2,4′-MDI and TDI and a polyol essentially including a polyether polyol,
Or
Mixtures of reaction products of 4,4'-MDI essential, each of at least one isocyanate component from the group consisting of 2,4'-MDI and TDI, and a polyol wherein at least one of the polyols is a polyether polyol It is.

That is, examples of the urethane prepolymer (a) used in the present invention include (a1) to (a6).
(A1) A reaction product of 4,4′-MDI, 2,4′-MDI, and a polyol essentially comprising a polyether polyol.
(A2) A reaction product of 4,4′-MDI, TDI, and a polyol essentially comprising a polyether polyol.
(A3) A reaction product of 4,4′-MDI, 2,4′-MDI, TDI, and a polyol essentially comprising a polyether polyol.
(A4) A mixture of a reaction product 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 a plurality of reaction products are mixed, the polyether polyol may be at least one of the polyols used.
That is, for example, in the case of (a4), the following aspects are included.
(A4-1) A mixture of a reaction product of 4,4′-MDI and a polyol essentially comprising a polyether polyol and a reaction product of a polyol other than 2,4′-MDI and a polyether polyol.
(A4-2) A mixture of a reaction product of 4,4′-MDI and a polyol other than a polyether polyol and a reaction product of 2,4′-MDI and a polyol essentially comprising a polyether polyol.
The “polyol having a polyether polyol as an essential component” may be only a polyether polyol or a combination of a polyether polyol and a polyol other than the polyether polyol. Therefore, (a4-1) further includes the following aspects.
(A4-1-1) A mixture of a reaction product of 4,4′-MDI and a polyether polyol and a reaction product of a polyol other than 2,4′-MDI and a polyether polyol.
(A4-1-2) A mixture of a reaction product of 4,4′-MDI and a polyol other than polyether polyol and a reaction product of 2,4′-MDI and polyether polyol.
(A4-1-3) A mixture of a reaction product of 4,4′-MDI and a polyether polyol and a reaction product of 2,4′-MDI and a polyether polyol.

In the case of (a1) to (a3), 4,4′-MDI, 2,4′-MDI and the like can be mixed, and then reacted with a polyol which requires polyether polyol as an essential component. It is also possible to react the isocyanate in turn with a polyol which essentially requires a polyether polyol.

  Furthermore, the reaction products (a1) to (a3) are used together, the mixtures (a4) to (a6) are used together, the reaction products (a1) to (a3) and (a4) to (a It can also be used in combination with the mixture of a6).

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

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

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

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

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

As described above, the polyisocyanate component (A) in the present invention includes 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. And at least one isocyanate monomer. The isocyanate monomer may be the remaining unreacted isocyanate monomer when the urethane prepolymer (a) is obtained, or may be added after obtaining the urethane prepolymer (a).
The polyisocyanate component (A) preferably has a number average molecular weight of 200 to 800, more preferably 300 to 700. Although the polyisocyanate component (A) contains the urethane prepolymer (a), it preferably has a molecular weight as described above by containing an isocyanate monomer.

Moreover, it is preferable that the polyisocyanate component (A) used for this invention contains 10 mass% or more and less than 18 mass% of isocyanate groups.
When the isocyanate group content of the polyisocyanate component (A) is within the above range, a laminate having a better appearance can be formed when a film base material having a high gas barrier property is used. The isocyanate group content (% by mass) is determined by titration with hydrochloric acid as described later.

The ratio of 4,4′-MDI, 2,4′-MDI and TDI contained in the polyisocyanate component (A) is the sum of 4,4′-MDI, 2,4′-MDI and TDI. In 100 mol%,
4,4′-MDI is 30 mol% or more and 70 mol% or less,
2,4′-MDI is 30 mol% or more and 70 mol% or less,
It is preferable that TDI is 30 mol% or more and 70 mol% or less.
When the composition ratio of the two types of MDI is in the above range, the coating appearance of the ink part in the laminate can be improved and good adhesion performance can be exhibited without managing the aging temperature to 40 ° C. or higher. When only 2,4′-MDI or TDI is used, sufficient adhesive performance cannot be exhibited by short-time aging. On the other hand, when only 4,4′-MDI is used, the appearance of the ink part in the laminate is not sufficiently improved.

Next, the polyol component (B) contained in the adhesive composition in the present invention will be described.
The polyol component (B) essentially comprises a polyester polyol having a number average molecular weight of 500 or more and 3,000 or less, 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 number average. It may further include at least one selected from the group consisting of polyether polyols having a molecular weight of 500 or more and 10,000 or less.
Adequate adhesive strength can be obtained by using polyester polyol as an essential component. Further, by containing at least one selected from the group consisting of a diol having a number average molecular weight of 50 or more and less than 500, a triol having a number average molecular weight of 50 or more and less than 500, and a polyether polyol having a number average molecular weight of 4500 or more and 10,000 or less, Strength under humidity is improved.

A polyester polyol having a number average molecular weight of 500 or more and 3000 or less used as an essential component of the polyol component (B) will be described.
Examples of the polyester polyol include polyvalent carboxylic acids such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, and sebacic acid, or dialkyl esters thereof or mixtures thereof, and, for example, ethylene glycol, propylene glycol, diethylene glycol, butylene glycol. , Neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3′-dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, and other glycols Lactones such as polyester polyols or polycaprolactones, polyvalerolactones, poly (β-methyl-γ-valerolactones) obtained by reacting them with a mixture thereof Polyester polyols obtained by ring-opening polymerization.
In addition, polyester oil-derived polyester compounds such as vegetable oil and vegetable oils can be used.

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

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

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

  As the polyether diol, for example, an oxirane compound such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran and the like obtained by polymerizing, for example, water, ethylene glycol, propylene glycol and the like bifunctional low-part polyols as initiators. And ether diol.

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

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

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

Examples of the polycarbonate diol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, and 1,9-nonane. Diol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1
, 4-cyclohexanediol, 1,4-cyclohexanedimethanol, one or two or more glycols selected from a reaction with dimethyl carbonate, diphenyl carbonate, ethylene carbonate, phosgene, etc. It is done.

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

  Examples of the polyether triol include polyether triols obtained by polymerizing oxirane compounds such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran, for example, using low-part triols such as trimethylolpropane and glycerin as an initiator. .

  As the polyether polyol used as a polyether diol having a number average molecular weight of 500 or more and less than 10,000, for example, oxirane compounds such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, etc., for example, water, ethylene glycol, propylene glycol, trimethylolpropane And polyether polyols obtained by polymerization using a low molecular weight polyol such as glycerin as an initiator.

The polyol component (B) is a polyester polyol having a number average molecular weight of 500 or more and 3,000 or less in a proportion of 100% by weight of the polyol component (B). 60% by weight or more and 99% by weight or less, 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 10,000 or less, preferably 1% by mass or more and 40% by mass or less.
A combination of diol, triol, and polyether diol is within the above range, so that a laminate having a better appearance can be obtained when a film base material having a high gas barrier property is used for coating and bonding at high speed. be able to.

  The polyol component (B) includes the diol having a number average molecular weight of 50 or more and less than 500, a triol having a number average molecular weight of 50 or more and less than 500, and a polyether polyol having a number average molecular weight of 4500 or more and 10,000 or less. Other polyol components can be included as long as the purpose is not impaired.

In the adhesive composition according to the present invention, when the number of hydroxyl groups in the polyol component (B) is 100 moles, the number of moles of isocyanate groups in the polyisocyanate component (A) is 120 to 300 moles. It is preferable.
When the number of hydroxyl groups in the polyol component (B) is 100 moles, the number of moles of isocyanate groups in the polyisocyanate component (A) is within the above range. Adhesive strength can be expressed.

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

The adhesive composition in the present invention has an average particle size of 1 × 10 ⁻⁴ mm or more and 4 × 10 ⁻⁴ m.
m or less particles can be further contained. By containing particles having an average particle diameter within the above range, a film substrate having a high gas barrier property can be used to obtain a laminate having a more external appearance when coating and laminating at high speed. If the particles are too small, the flow characteristics will not change much even if added, so the appearance will not change much.
Here, the average particle diameter is an average volume diameter and is a value obtained by a laser light scattering method.

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

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

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

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

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

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

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

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

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

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

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

The white ink layer is a dried or cured product of the aforementioned white ink composition containing a polyurethane polyurea resin having a specific hydroxyl group and a specific amount of an amino silane coupling agent.
The white ink layer can be obtained by printing a white ink composition on the transparent substrate 1 and drying or curing. The white ink composition can be printed by a known printing method such as gravure printing or flexographic printing, but is particularly preferably printed by a gravure printing method. As the cylinder used for gravure printing, known ones such as engraving type and corrosion type are used.
A white ink composition diluted with a diluting solvent to a viscosity and concentration suitable for gravure printing is supplied to each printing unit alone or mixed, passed through an oven after printing, dried or cured, and then white ink A layer is formed. The oven temperature is usually 40 to 80 ° C., and the printing speed is usually 50 to 300 m / min. In winter when the printing environment is low, the ink composition is cured by reliably proceeding with the crosslinking reaction with the amino-based silane coupling agent. It is preferable to coat or to overlap the white ink layer and the precursor of the adhesive layer. The white ink layer is usually 0.5 to 5 g / m ² and preferably ¹ to 3.5 g / m ² .

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

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

Moreover, the vapor deposition film which vapor-deposited aluminum, silicon oxide, aluminum oxide, etc. on the various plastic films can also be used as the base material 2. In many cases, the thickness of the vapor deposition layer is about 1 to 500 nm. By providing such a vapor deposition layer, the influence of the type and thickness of the plastic film on the oxygen permeability is extremely small.
For example, an unstretched polypropylene film provided with an aluminum vapor deposition layer has an oxygen permeability of 20 to 10 (CC / m ² · 24 h · atm, at 25 ° C.),
A polyethylene terephthalate film provided with an aluminum vapor deposition layer has an oxygen permeability of ^{2 to} 0.3 (CC / m ² · 24 h · atm, at 25 ° C.),
A polyethylene terephthalate film provided with a vapor deposition layer of aluminum oxide has an oxygen permeability of 4 to 0.5 (CC / m ² · 24 h · atm, at 25 ° C.),
A polyethylene terephthalate film provided with a silicon oxide vapor-deposited layer has an oxygen permeability of 5 to 0.3 (CC / m ² · 24 h · atm, at 25 ° C.) and is used as the substrate 2.
Moreover, as metal foil, metal foils, such as stainless steel, iron, copper, and lead, have an oxygen permeability of 0 (CC / m ² · 24 h · atm, at 25 ° C.) regardless of the thickness.
The substrate 2 is preferably a plastic film provided with a vapor deposition layer on various plastic films or a metal foil, and particularly a metal vapor deposited on various plastic films (hereinafter sometimes referred to as vapor deposition film). The metal deposition layer is preferably in contact with the adhesive layer.

The oxygen permeability can be determined according to the method of JIS K 7126 using an oxygen permeability measuring device.
For example, Mocon oxygen permeability measuring device (OX-TR) manufactured by Hitachi High-Technologies Corporation
AN2 / 21) is a device equipped with a coulometric sensor that generates a current proportional to the amount of oxygen that has passed through the sample by means of a carrier gas (nitrogen), measures the voltage change through a standard load resistance, and determines the oxygen permeability. Convert.

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

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

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

<Method for measuring acid value>
About 1 g of a sample was accurately weighed in a stoppered Erlenmeyer flask and dissolved by adding 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution. To this was added a phenolphthalein test solution as an indicator, which was held for 30 seconds, and then titrated with a 0.1N alcoholic potassium hydroxide solution until the solution turned light red. The acid value was determined by the following (Formula 3). The acid value is a numerical value of the dry state of the resin (unit: mgKOH / g)
(Formula 2) Acid value (mgKOH / g) = {(5.611 × a × F) / S} / (Nonvolatile content concentration / 100)
Where S: Amount of sample collected (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution

<Method for measuring NCO content (% by weight)>
About 1 g of a sample was precisely weighed 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 therein. To this was added a phenolphthalein test solution as an indicator, which was kept for 30 seconds, and then titrated with a 0.25N hydrochloric acid solution until the solution became light red. NCO (mass%) was determined by the following (formula 4).
(Formula 3) NCO (mass%) = {(ba) × 4.202 × F × 0.25} / S
S: Sample collection amount (g)
a: Consumption of 0.25N hydrochloric acid solution (ml)
b: Consumption (ml) of consumption (ml) of 0.25N hydrochloric acid solution in the empty experiment
F: Potency of 0.25N hydrochloric acid solution

(Synthesis of polyurethane polyurea resin for ink composition)
[Synthesis Example 1-1]
To a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas introduction tube, polyester polyol A1 (a copolymer of Kuraray polyol P-2010, 3-methyl-1,5-pentanediol and adipic acid, several Average molecular weight 2000, manufactured by Kuraray Co., Ltd.) 11.36 parts, polyether polyol B (EXCENOL 2020, propylene oxide polymer, number average molecular weight 2000, manufactured by Asahi Glass) 11.36 parts, isophorone diisocyanate (hereinafter also abbreviated as IPDI) 5.05 Parts, 4.36 parts of ethyl acetate, 0.003 part of 2-ethylhexanoate, and allowed to react at 90 ° C. for 5 hours under a nitrogen stream.
A solution of a urethane prepolymer having an isocyanate group at the terminal was obtained.
Next, 1.92 parts of isophoronediamine (hereinafter also abbreviated as IPDA), 0.01 part of 2-hydroxyethylethylenediamine, 0.29 part of di-n-butylamine, 30.147 parts of ethyl acetate, and isopropyl alcohol (hereinafter also abbreviated as IPA) 28 The obtained urethane prepolymer solution was gradually added to a mixture of parts at room temperature, then reacted at 50 ° C. for 1 hour, solid content 30%, mass average molecular weight 50000, hydroxyl value 0.1 mg KOH / resin 1 g of polyurethane polyurea resin solution (PU1) was obtained.
In addition, in this synthesis example, the solution of the urethane prepolymer obtained by amines is dripped, and chain extension reaction is performed.

[Synthesis Examples 1-2 to 1-4]
A polyurethane polyurea resin solution (PU2 to PU4) was obtained in the same manner as in Synthesis Example 1-1 at the charging ratio shown in Table 1.

[Synthesis Example 1-5]
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 11.67 parts of polyester polyol A1, 11.67 parts of polyether polyol B, isophorone diisocyanate (hereinafter also abbreviated as IPDI). ) 5.19 parts, ethyl acetate 4.36 parts, 2-ethylhexanoic acid 0.003 parts were charged and reacted at 90 ° C. for 5 hours under a nitrogen stream, and 7.5 parts of ethyl acetate was added and cooled. A solution of a urethane prepolymer having an isocyanate group was obtained.
Subsequently, 1.23 parts of isophorone diamine (hereinafter also abbreviated as IPDA), 0.16 part of 2-hydroxyethylethylenediamine, 0.07 part of monoethanolamine, 30.147 parts of ethyl acetate and the resulting urethane prepolymer solution A mixture of 28 parts of isopropyl alcohol (hereinafter also abbreviated as IPA) is gradually added at room temperature, followed by reaction at 50 ° C. for 1 hour, polyurethane having a solid content of 30%, a weight average molecular weight of 50000, a hydroxyl value of 5 mg KOH / resin of 1 g of polyurethane. A polyurea resin solution (PU5) was obtained.
In this synthesis example, amines were dropped into the obtained urethane prepolymer solution to carry out a chain extension reaction.

[Synthesis Example 1-6]
Synthetic Example 1-1, except that 11.45 parts of polyester polyol A2 (Teslac 2459, copolymer of ethylene glycol and adipic acid, number average molecular weight 2000, manufactured by Hitachi Chemical Co., Ltd.) is used instead of polyester polyol A1. A polyurethane polyurea resin (PU6) was obtained in the same manner as in.

[Synthesis Example 1-7]
A polyurethane polyurea resin solution (PU7) was obtained in the same manner as in Synthesis Example 1-5 at the composition ratio shown in Table 2.

[Synthesis Example 1-8]
A polyurethane polyurea resin solution (PU8) was obtained in the same manner as in Synthesis Example 1-1 at the composition ratio preparation ratio shown in Table 2.

(Preparation of ink composition)
[Production Example 1-1]
10 parts of polyurethane polyurea resin solution (PU1), 30 parts of titanium oxide (TITONE R45M, manufactured by Sakai Chemical Co., Ltd.) and 10 parts of ethyl acetate / IPA mixed solvent (mass ratio 75/25) were stirred and mixed in a sand mill. After stirring and mixing 40 parts of a polyurea resin solution (PU1), 10 parts of an ethyl acetate / IPA mixed solution (mass ratio 75/25) and 0.5 part of an amino silane coupling agent (Si-1), methyl ethyl ketone, normal propyl The mixture was diluted with a mixed solvent of acetate and IPA (mass ratio: 40:40:20), adjusted to 15 seconds with Zahn Cup # 3 (manufactured by Kosei Co., Ltd.), and ink composition (i-1) was obtained. The content of the amino silane coupling agent in the solid content of 100% by mass of the ink composition is 1.1% by mass.
The amino silane coupling agents used are as follows.
Si-1: 3-aminopropyltrimethoxysilane

[Production Examples 1-2 to 1-12] and [Production Examples 1-14 to 20]
Ink compositions (i-2 to i-12, i-14 to i-20) were obtained in the same manner as in Production Example 1-1 with the charging ratios in Tables 3 and 4. The amino silane coupling agents and isocyanic curing agents used are as follows.
Si-2: N-phenyl-3-aminopropyltrimethoxysilane Si-3: 3-aminopropylmethyldiethoxysilane Si-4: Bis (3-trimethoxysilylpropyl) amine Si-5: N-2- ( Aminoethyl) -3-aminopropyltrimethoxysilane Si-6: hexyltrimethoxysilane N-1: SP curing agent (isocyanic curing agent, manufactured by Toyo Ink)

[Production Example 13]
10 parts of polyurethane polyurea resin solution (PU3), 30 parts of titanium oxide (TITONE R45M, manufactured by Sakai Chemical), 9.5 parts of ethyl acetate / IPA mixed solvent (mass ratio 75/25), amino silane coupling agent (Si- 1) After stirring and mixing 0.5 part and kneading with a sand mill, 40 parts of polyurethane polyurea resin solution (PU3) and 10 parts of ethyl acetate / IPA mixed solution (mass ratio 75/25) were stirred and mixed, and then methyl ethyl ketone, The mixture was diluted with a mixed solvent of normal propyl acetate and IPA (mass ratio 40:40:20), adjusted to 15 seconds with Zahn Cup # 3 (manufactured by Kosei Co., Ltd.), and ink composition (i-13) was obtained.

Synthesis of polyisocyanate component (A) for adhesive composition (Synthesis Example 101)
300 parts of polypropylene glycol having a number average molecular weight of about 400 (hereinafter referred to as PPG-400), 400 parts of polypropylene glycol having a number average molecular weight of about 2000 (hereinafter referred to as PPG-2000), and about 400 having a number average molecular weight obtained by adding polypropylene glycol to glycerin. 200 parts of triol (hereinafter referred to as PPG-400-3 functional), 400 parts of 4,4′-MDI and 600 parts of 2,4-MDI were charged in a reaction vessel at 70 ° C. to 80 ° C. while stirring under a nitrogen gas stream. A urethanization reaction was performed by heating for 3 hours to obtain a polyether polyurethane polyisocyanate resin having an isocyanate group with an isocyanate group content of 14.4% and an MDI monomer content of 33%. Hereinafter, this resin is referred to as polyisocyanate A1- (1).

(Synthesis Examples 102-103)
According to the composition shown in Table 5, polyisocyanate A1- (2) and A1- (3), which are polyether polyurethane polyisocyanate resins, were obtained in the same manner as in Synthesis Example 1.

(Synthesis Example 4)
80 parts of isophthalic acid, 460 parts of adipic acid, 60 parts of 1,6 hexanediol, and 400 parts of diethylene glycol were charged into a reaction vessel and heated to 150 ° C. to 240 ° C. while stirring under a nitrogen gas stream to conduct an esterification reaction. . When the acid value reached 1.3 (mg KOH / g), the reaction temperature was set to 200 ° C., the pressure inside the reaction vessel was gradually reduced, and the reaction was carried out at 1.3 kPa or less for 30 minutes to give an acid value of 0.4 (mg KOH / g ), A hydroxyl group value of 80 (mgKOH / g), and a number average molecular weight of about 1400, a polyester diol resin having hydroxyl groups at both ends 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 charged into a reaction vessel and stirred at 70 ° C. under a nitrogen gas stream. A urethanation reaction was performed by heating at -80 ° C for 3 hours to obtain a polyether polyurethane polyisocyanate resin having an isocyanate group with an isocyanate group content of 17% and an MDI monomer content of 48%. Hereinafter, this resin is referred to as polyisocyanate A1- (4).

(Synthesis Example 105)
200 parts of PPG-400, 200 parts of castor oil, 145 parts of TDI, charged in a reaction vessel, heated at 80 ° C. for 1 hour with stirring under a nitrogen gas stream, and subjected to a urethanization reaction. -MDI: 178 parts and 2,4-MDI: 192 parts were added, and the mixture was heated at 80 ° C. for 3 hours with stirring under a nitrogen gas stream to carry out a urethanation reaction. The isocyanate group content was 16.1%, MDI A polyether polyurethane polyisocyanate resin having an isocyanate group with a monomer content of 37% was obtained. 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 charged into a reaction vessel and heated to 150 ° C. to 240 ° C. while stirring under a nitrogen gas stream to conduct an esterification reaction. When the acid value reached 1.3 (mgKOH / g), the reaction temperature was set to 200 ° C., the pressure inside the reaction vessel was gradually reduced, and the reaction was carried out at 1.3 kPa or less for 30 minutes to give an acid value of 0.5 (mgKOH / g ), A hydroxyl group value of 56.1 (mgKOH / g) and a number average molecular weight of about 2000, a polyester diol resin having hydroxyl groups at both ends was obtained.
70 parts of the obtained polyester resin, 367 parts of PPG-400, 265 parts of TDI, charged in a reaction vessel, and heated at 80 ° C. for 1 hour with stirring under a nitrogen gas stream to conduct a urethanization reaction, 4,4′-MDI: 286 parts were added, and urethanation reaction was carried out by heating at 80 ° C. for 3 hours while stirring under a nitrogen gas stream. The isocyanate group content was 12% and the MDI monomer content was 27%. A polyether polyurethane polyisocyanate resin having an isocyanate group was obtained. 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 charged into a reaction vessel and stirred at 80 ° C. with stirring under a nitrogen gas stream. A urethanization reaction was performed by heating for a time to obtain a polyether polyurethane polyisocyanate resin having an isocyanate group having an isocyanate group content of 15.4% and an MDI monomer content of 34%. Hereinafter, this resin is referred to as polyisocyanate A1- (7).

(Synthesis Example 108)
300 parts of PPG-400, 400 parts of PPG-2000, 200 parts of PPG-400-3 functionality, and 1000 parts of 4,4′-MDI: 1000 parts were charged in a reaction vessel at 80 ° C. with stirring under a nitrogen gas stream. A urethanization reaction was performed by heating for 3 hours to obtain a polyether polyurethane polyisocyanate resin having an isocyanate group with an isocyanate group content of 14.4% and an MDI monomer content of 33%. Hereinafter, this resin is referred to as polyisocyanate A1- (8).

(Synthesis Example 109)
607 g of xylylene diisocyanate (hereinafter referred to as XDI), 672 g of butylene adipate (Takelac U-2410, manufactured by Takeda Pharmaceutical Co., Ltd.) having crystallinity at room temperature and a molecular weight of about 1,000. 156 g of 3-functional polypropylene glycol (Accor 32-160, manufactured by Takeda Pharmaceutical Co., Ltd.) and 0.6 g of benzoyl chloride were charged into the reactor, respectively, and subjected to urethanization reaction at 70-80 ° C under nitrogen flow. After completion, 389 g of polyisocyanate (Takeda Pharmaceutical Co., Ltd., Takenate D-170HN), which is a modified polymer of an aliphatic polyisocyanate, is added and mixed uniformly at 70 to 80 ° C. under a nitrogen stream. Rate is 6.3%, XD
A polyisocyanate component having an I monomer content of 13% and an MDI monomer content of 0% was obtained. Hereinafter, this resin is referred to as polyisocyanate A1- (9).

Synthesis of polyol component (B) for adhesive composition (Synthesis Example 201)
A reaction vessel was charged with 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). While stirring under gas flow 1
The esterification reaction was performed by heating to 50 ° C to 240 ° C. When the acid value reached 1.3 (mg KOH / g), the reaction temperature was set to 200 ° C., the pressure inside the reaction vessel was gradually reduced, and the reaction was carried out at 1.3 kPa or less for 30 minutes to give an acid value of 0.4 (mg KOH / g ), A hydroxyl group value of 137 (mgKOH / g) and a number average molecular weight of about 800, a polyester diol resin having hydroxyl groups at both ends was obtained. Hereinafter, this polyol is referred to as polyester diol (b1) -1.

(Synthesis Examples 202 to 207)
According to the composition shown in Table 6, polyester diols (b1) -2 to (b1) -7 were obtained in the same manner as in Synthesis Example 201.

(Formulation example 301)
Polyester diol (b1) -1 obtained in Synthesis Example 201: 92 parts and diethylene glycol: 8 parts were mixed to obtain polyol component B- (1).

(Formulation examples 302 to 317)
According to the composition shown in Table 7, polyol components B- (2) to B- (10) were obtained in the same manner as in Formulation Example 301.

(Production example 401)
100 parts of the polyisocyanate component A- (1) obtained in Synthesis Example 101 and 50 parts of the polyol component B- (1) obtained in Formulation Example 301 were mixed at 60 ° C. to obtain a solventless adhesive composition AD1. Obtained.
In addition, the said solventless type adhesive composition AD1 contains 182 mol of isocyanate groups derived from polyisocyanate component A- (1) with respect to 100 mol of hydroxyl groups in the polyol component.
The amount of the isocyanate group with respect to 100 mol of the hydroxyl group is determined as follows.
Amount of isocyanate group per 100 mol of hydroxyl group = [isocyanate group (eq.) / Hydroxyl group (eq.)] × 100
Isocyanate group (eq.) = NCO content (mass%) / (42 × 100)
Hydroxyl group (eq.) = Hydroxyl value / 56100

The total ratio of 4,4′-MDI, 2,4′-MDI, 2,2′-MDI and TDI (hereinafter referred to as isocyanate monomer) contained in 100% of the solventless adhesive composition is: 22%.
The isocyanate monomer content is the total area of the peak area derived from the MDI monomer near Mn = 200 to 300 and the peak area derived from the TDI monomer near Mn = 100 to 200, which is observed on the GPC chart, on the GPC chart. Divided by the total area of all peaks observed.
Isocyanate monomer content (%) = (total peak area of isocyanate monomer / total area of all peaks) × 100

(Production Examples 402 to 416)
According to the composition shown in Table 8, adhesive composition AD2-AD16 was obtained in the same manner as in Production Example 401.

[Examples 1 to 13], [Comparative Examples 1 to 7]
[Production of printed matter]
The ink compositions i-1 to i-20 obtained in Production Examples 1 to 20 were subjected to a corona-treated PET as a transparent substrate 1 at a printing speed of 50 m / min by a gravure printing machine equipped with a gravure plate having a plate depth of 30 μm. It printed on the film (Toyobo ester film E5100 # 12), and it dried or hardened by passing through 60 degreeC oven, and formed the ink layer on PET film.

[Production of laminate]
Using a solventless test coater, the solventless adhesive composition AD1 obtained in Production Example 401 was applied to the surface of the ink layer printed on the PET film at a temperature of 60 ° C. and a coating speed of 200 m / min. (Coating amount: 2 g / m ² ) An oxygen-deposited unstretched polypropylene film (hereinafter referred to as VMCPP) having an oxygen permeability of 20 (CC / m 2 · 24 h · atm, at 25 ° C.) on the coated surface. Thickness: 25 μm. ) Was deposited, and a layered product (pre-layered product) at a preparation stage was obtained.
These pre-laminated bodies were aged in an environment of 25 ° C. and 80% RH for 1 day to cure the adhesive layer, thereby preparing a laminated body. About the obtained laminated body, the adhesive force of the laminated body and the interface state of the laminated body were evaluated according to the following method. The results are shown in Table 9.

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

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

As shown in Table 9, it contains a polyurethane polyurea resin having a hydroxyl group of 0.1 to 20 (mgKOH / g), and an amino silane coupling agent is added in an amount of 0.15 to 7 in 100% by mass of the solid content of the ink composition. In Examples 1 to 13 using a white ink composition containing% by mass, since the amine-based silane coupling agent crosslinks the polyurethane polyurea resin and the white inorganic pigment, 4,4′-MDI or the like to the ink layer, The penetration of isocyanate monomer can be suppressed. As a result, as compared with Comparative Examples 1 to 6, the appearance and adhesive strength after aging at 25 ° C. for 1 day are excellent.
Since Comparative Example 1 uses an ink composition containing a polyurethane polyurea resin having a hydroxyl value of 21 mgKOH / g, the cohesive strength of the ink layer is inferior, and 4,4′-MDI or the like in the adhesive composition Penetration cannot be prevented, resulting in poor appearance.
Since Comparative Example 2 uses an ink composition containing a polyurethane polyurea resin having a hydroxyl group of 0 mg KOH / g, crosslinking with an amino-based silane coupling agent cannot be performed, resulting in poor appearance.
In Comparative Example 3, since the amino-based silane coupling agent contains only 0.1% by mass in 100% by mass of the solid content of the ink composition, crosslinking with the coupling agent is insufficient and the appearance is not improved.
In Comparative Example 4, since the amino silane coupling agent is excessively contained (7.8% by mass in 100% by mass of the solid content of the ink composition), the amino coupling agent and the adhesive that do not participate in crosslinking are used. Since the isocyanate component reacts, the reaction between the hydroxyl component and the isocyanate component in the adhesive becomes insufficient, and the laminate strength of the laminate is lowered. In addition, the amino-based silane coupling agent transferred to the adhesive layer promotes the reaction of the adhesive as a basic catalyst, and the adhesive leveling property during the curing of the adhesive is reduced, so the appearance is not sufficient. .
Comparative Example 5 has a poor appearance because no amino-based silane coupling agent is added.
In Comparative Example 6, not an amino silane coupling agent but an alkyl silane coupling agent was added, and it was confirmed that the appearance was not improved.
In Comparative Example 7, an isocyanate curing agent is added to the ink, and the appearance is poor even when the isocyanate curing agent is added. Probably, amino-based silane coupling agents have two types of functional groups, an amino group and a silanol group, which not only can react with both the polyurethane polyurea resin and the pigment, but also the amino group by reacting the silanol group with the pigment. It is considered that the particles are oriented on the outside of the pigment, the affinity with the polyurethane polyurea resin is improved, and the pigment is uniformly dispersed, so that the binder and the pigment can be uniformly crosslinked uniformly. .

[Examples 14 to 24] [Comparative Examples 8 to 11]
As shown in Table 10, solvent-free adhesive compositions AD2 to 16 obtained in Production Examples 402 to 416 were used instead of the adhesive composition AD1 using i-3 instead of the ink composition i-1. A laminate was obtained in the same manner as in Example 1 except that was used, and evaluated in the same manner. The results are shown in Table 10.

As shown in Table 10, it can be seen that Examples 14 to 24 in which the adhesive layer was formed with the adhesive composition of the present invention were excellent in appearance and adhesive strength after aging at 25 ° C. for 1 day.
In contrast, Comparative Example 8 is an isocyanate component A1- containing a urethane prepolymer (a) obtained by using only 4,4′-MDI and 4,4′-MDI as the isocyanate component (A). Since (8) is used, the reaction rate is too fast and the leveling property of the adhesive layer during curing is lowered, so that the appearance is not sufficient.
In Comparative Example 9, since polyester polyol B- (9) having a mass average molecular weight of 4000 was used as the polyol component (B), the reactivity with the isocyanate component (A) after coating was reduced, and 4 to the ink layer was reduced. , 4′-MDI or the like, and the appearance of the ink film is broken due to the penetration of the isocyanate monomer.
In Comparative Example 10, since 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 high, and the adhesive layer during curing was leveled. The appearance is not sufficient because the properties are reduced.
In Comparative Example 11, the isocyanate component A1- (9) component derived from XDI and HDI is used as the isocyanate component (A), and the strength after one day of aging at 25 ° C. is not sufficient because the curing rate is slow.

[Examples 25 to 36] [Comparative Examples 12 to 18]
As shown in Table 11, a laminate was obtained by operating in the same manner as in Example 1 except that the solventless adhesive composition AD10 obtained in Production Example 410 was used instead of the adhesive composition AD1. , And evaluated in the same manner. The results are shown in Table 11.

  From Table 11, it can be confirmed that even if the adhesive composition is changed, it tends to be the same as in Table 9.

(Production example 401)
100 parts of the polyisocyanate component A 1- (1) obtained in Synthesis Example 101 and 50 parts of the polyol component B- (1) obtained in Formulation Example 301 are mixed at 60 ° C., and a solventless adhesive composition AD1. Got.
Incidentally, the solvent-free adhesive composition AD1 is hydroxyl in the polyol component: to 100 moles, polyisocyanate component A 1 - (1) derived from isocyanate groups to 182 molar content.
The amount of the isocyanate group with respect to 100 mol of the hydroxyl group is determined as follows.
Amount of isocyanate group per 100 mol of hydroxyl group = [isocyanate group (eq.) / Hydroxyl group (eq.)] × 100
Isocyanate group (eq.) = NCO content (mass%) / (42 × 100)
Hydroxyl group (eq.) = Hydroxyl value / 56100

Claims (6)

A laminate having a transparent substrate 1, a white ink layer, an adhesive layer, and a substrate 2 having an oxygen permeability of 100 (CC / m 2 · 24h · atm, at 25 ° C) or less in this order,
A laminate that satisfies all the following conditions (1) to (3) for the white ink layer and the following conditions (11) to (15) for the adhesive layer.
(1) The white ink layer is a dried or cured product of a white ink composition containing a polyurethane polyurea resin, a white inorganic pigment, an amino silane coupling agent, and an organic solvent.
(2) The polyurethane polyurea resin has a hydroxyl group of 0.1 to 20 (mgKOH / g).
(3) 0.15-7 mass% of said amino-type silane coupling agent is contained in 100 mass% of solid content of an ink composition.

(11) The adhesive layer is a cured product of an adhesive composition containing a polyisocyanate component (A) and a polyol component (B).
(12) The polyisocyanate component (A) includes 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 tolylene diisocyanate. And at least one isocyanate.
(13) The urethane prepolymer (a) having the isocyanate group is
A reaction product of an isocyanate component essentially comprising 4,4′-diphenylmethane diisocyanate and further comprising at least one from the group consisting of 2,4′-diphenylmethane diisocyanate and tolylene diisocyanate, and a polyol essentially comprising a polyether polyol. Is there
Or
4,4′-diphenylmethane diisocyanate is essential, and is a mixture of at least one isocyanate component from the group consisting of 2,4′-diphenylmethane diisocyanate and tolylene diisocyanate and a reaction product of a polyol, One is a mixture that requires a polyether polyol.
(14) The polyol component (B) contains a polyester polyol having a number average molecular weight of 500 or more and 3000 or less as an essential component.
(15) The total amount of 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate and tolylene diisocyanate contained in 100% by mass of the adhesive composition is 10 to 34% by mass.   The laminate according to claim 1, wherein the amino-based silane coupling agent has a primary amino group, or has a secondary amino group and four or more alkoxy groups.   The laminated body of Claim 2 in which the silane coupling agent which has a primary amino group further has a secondary amino group among the said amino-type silane coupling agents.   The laminate according to any one of claims 1 to 3, wherein the substrate 2 has a metal vapor deposition layer on one surface, and the metal vapor deposition layer is in contact with the adhesive layer. A method for producing a laminate having, in this order, a transparent substrate 1, a white ink layer, an adhesive layer, and a substrate 2 having an oxygen permeability of 100 (CC / m 2 · 24h · atm, at 25 ° C) or less, The manufacturing method of the laminated body containing following process (I)-(VI).
(I) Polyurethane polyurea resin having a hydroxyl value of 0.1 to 20 (mgKOH / g), white inorganic pigment, organic solvent, and 0.15 to 7 in 100% by mass of the solid content of the ink composition
A step of preparing a white ink composition containing a mass% amino-based silane coupling agent.
(II-1) an isocyanate component essentially comprising 4,4′-diphenylmethane diisocyanate and further comprising at least one selected from the group consisting of 2,4′-diphenylmethane diisocyanate and tolylene diisocyanate, and a polyol essentially comprising a polyether polyol Is reacted under conditions of excess isocyanate groups,
Or
A condition in which 4,4′-diphenylmethane diisocyanate is essential, each of at least one isocyanate component from the group consisting of 2,4′-diphenylmethane diisocyanate and tolylene diisocyanate, and a polyol in which polyether polyol is essential, and an isocyanate group excess condition After reacting below, mix,
A urethane prepolymer (a) having an isocyanate group;
A polyisocyanate component (A) comprising 4,4′-diphenylmethane diisocyanate and further comprising at least one isocyanate selected from the group consisting of 2,4′-diphenylmethane diisocyanate and tolylene diisocyanate;
(II-2) The polyisocyanate component (A) and a polyol component (B) containing a polyester polyol having a number average molecular weight of 500 to 3000 as an essential component are mixed,
The total amount of 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate and tolylene diisocyanate contained in a total of 100 mass% of the polyisocyanate component (A) and the polyol component (B) is 10 to 10%. The process of preparing the adhesive composition which is 34 mass%.
(III) A step of applying the white ink composition to the transparent substrate 1 and drying or curing to obtain a white ink layer.
(IV) A step of applying the adhesive composition on the white ink layer to form a precursor of the adhesive layer.
(V) A step of stacking the base material 2 on the precursor of the adhesive layer.
(VI) A step of curing the precursor of the adhesive layer to form an adhesive layer.
A method for producing a laminate having, in this order, a transparent substrate 1, a white ink layer, an adhesive layer, and a substrate 2 having an oxygen permeability of 100 (CC / m 2 · 24h · atm, at 25 ° C) or less, The manufacturing method of the laminated body containing following process (I)-(III), (VII)-(IX).
(I) A polyurethane polyurea resin having a hydroxyl value of 0.1 to 20 (mgKOH / g), a white inorganic pigment, an organic solvent, and 0.15 to 7% by weight of amino in 100% by weight of the solid content of the ink composition A step of preparing a white ink composition containing a silane coupling agent.
(II-1) an isocyanate component essentially comprising 4,4′-diphenylmethane diisocyanate and further comprising at least one selected from the group consisting of 2,4′-diphenylmethane diisocyanate and tolylene diisocyanate, and a polyol essentially comprising a polyether polyol Is reacted under conditions of excess isocyanate groups,
Or
A condition in which 4,4′-diphenylmethane diisocyanate is essential, each of at least one isocyanate component from the group consisting of 2,4′-diphenylmethane diisocyanate and tolylene diisocyanate, and a polyol in which polyether polyol is essential, and an isocyanate group excess condition After reacting below, mix,
A urethane prepolymer (a) having an isocyanate group;
A polyisocyanate component (A) comprising 4,4′-diphenylmethane diisocyanate and further comprising at least one isocyanate selected from the group consisting of 2,4′-diphenylmethane diisocyanate and tolylene diisocyanate;
(II-2) The polyisocyanate component (A) and a polyol component (B) containing a polyester polyol having a number average molecular weight of 500 to 3000 as an essential component are mixed,
Total 100% by mass of the polyisocyanate component (A) and the polyol component (B)
A step of preparing an adhesive composition in which the total amount of 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate and tolylene diisocyanate is 10 to 34 mass%.
(III) A step of applying the white ink composition to the transparent substrate 1 and drying or curing to obtain a white ink layer.
(VII) A step of applying the adhesive composition on the base material 2 to form an adhesive layer precursor.
(VIII) A step of overlaying the white ink layer on the precursor of the adhesive layer.
(IX) A step of curing the adhesive layer precursor to form an adhesive layer.