JP6664845B2 - Laminate and manufacturing method thereof - Google Patents

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.

  Conventionally, the bonding of various plastic films and the bonding of a plastic film to a metal-deposited film or a metal foil have been performed by a dry lamination method using a hydroxyl group / isocyanate solvent-based adhesive composition. However, since the dry lamination method uses an adhesive composition containing an organic solvent, special equipment for suppressing and preventing environmental pollution and fire is required.

In recent years, there has been a strong demand for a decomposable organic solvent for an adhesive composition due to a demand for simple equipment, and research on solventless use 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.
Patent Document 2 discloses that a branch point concentration in a specific range containing a polyol component (1) and a polyisocyanate component (2) having a trifunctional polyisocyanate compound as an essential component, and the number of moles of hydroxyl group: isocyanate group A solventless laminating adhesive composition having a mole number of 1: 1 to 1: 3 is disclosed.
Patent Literature 3 discloses a solventless adhesive composition containing a polyol component (A) and an isocyanate component (B) essentially including 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) is composed of 2,4′-diphenylmethane diisocyanate (a1) and 4,4′-MDI (a2). Is a reactive product obtained by reacting a polyether polyol (a3) with a polyol essentially comprising a polyether polyol (a3), wherein the polyol component (B) has a number average molecular weight of 500 or more and 3000 or less. An adhesive composition containing polyester diol (b1) as essential and further containing at least one of diol (b2) and triol (b3) having a number average molecular weight of 50 or more and less than 500 is disclosed.
Further, in claim 2 of Patent Document 6, a polyethylene terephthalate film layer (F1) of an exterior, a dry film layer (P) of a printing ink, a dry film layer (C) of a coat resin, and a solventless adhesive layer (A ), A metal-deposited layer or metal foil (M), and a plastic film laminate having an interior plastic film layer (F2) in this order.
Patent Literature 7 discloses a two-part curable solventless adhesive composition containing a specific amount of a crystalline polyol component in the total amount of a polyol component (A) and a polyisocyanate component (B). .
Patent Document 8 discloses an adhesive containing a specific polyisocyanate component (A) containing a urethane prepolymer made from a polyether polyol as a raw material and crude MDI, and a specific polyol component (B) containing a polyesterdiol 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-A-2002-249745 Patent No. 5812219

  The 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 or a back side) of a transparent substrate. The printing ink layer will be seen from the opposite side (hereinafter, also referred to as the surface or 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.

The solvent-free adhesive composition has no drying step, no solvent is discharged, energy saving and good running cost, laminates after laminating plastic films, plastic film and metal foil or metal vapor deposition There are many merits such as that there is no concern that the solvent remains in the laminate after the layers are bonded.
However, when a laminate as a packaging material is formed using a solventless adhesive composition and a substrate having a high gas barrier property in which a metal deposition layer is provided on a film (hereinafter, also referred to as a barrier substrate). In addition, there is a problem that the appearance of a yuzu-skin-like appearance is easily generated on the ink portion. In particular, poor appearance is likely to occur on the white ink portion.

Patent Literatures 1 to 4 disclose that as the polyisocyanate component, one having a relatively mild reaction, specifically, an alicyclic polyisocyanate component or an aliphatic polyisocyanate component is used. However, a polyisocyanate component having a relatively mild reaction has a problem that the aging step requires 2 to 5 days at 40 to 50 ° C.
Further, Patent Documents 1 to 4 do not describe improvement of appearance defects in an ink portion.
In addition, the aging step means “the step of promoting the curing of the adhesive layer”.

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

Patent Documents [0013] and [0014] disclose a case in which a dry coating layer (P) of printing ink is provided between a polyethylene terephthalate film layer (F1) of an exterior and a dry coating layer (C) of a coat resin. It is disclosed that the coating resin constituting the dried film layer (C) of the coating resin uses a binder for printing ink to improve the appearance of the ink portion.
However, the processing speed specifically shown in the examples, that is, the coating speed of the adhesive was only 10 m / min. And slow. Since the solvent-free adhesive composition is solvent-free, if the coating speed is increased so far, the coated surface becomes rough, so that it has not been possible to achieve both improvement in coating speed and improvement in appearance. From the viewpoint of improving the productivity, a laminate having a good appearance of the ink portion is desired for the solventless adhesive composition at the same level as the solvent 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, even at a coating speed of 200 m / min, an attempt is made to improve the appearance of the ink portion. ing.
However, since the crystalline polyester is used, poor appearance cannot be improved by low-temperature aging at 40 ° C. or lower.

  Patent Document 8 discloses 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 and in a short time. Was rare.

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

The present invention has been made in view of the above problems, and the present invention relates to a laminate having a transparent substrate 1, a specific white ink layer, a specific adhesive layer, and a substrate 2 in this order. .
That is, the white ink layer constituting the laminate of the present invention satisfies all of the following conditions (1) to (3), and the adhesive layer satisfies all of the following conditions (11) to (17).
(1) The white ink layer is a dried or cured white ink composition containing a polyurethane polyurea resin, a white inorganic pigment, an amino-based silane coupling agent, and an organic solvent.
(2) The hydroxyl group of the polyurethane polyurea resin is 0.1 to 20 (mgKOH / g).
(3) The amino-based silane coupling agent is contained in an amount of 0.15 to 7% by mass based on 100% by mass of the solid content of the 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) contains a urethane prepolymer (a) having an isocyanate group and 4,4′-diphenylmethane diisocyanate.
(13) The polyisocyanate component (A) is composed of a trimer of a bifunctional isocyanate monomer, a burette in which water is added to a difunctional isocyanate monomer, and an adduct in which a monoalcohol is added to a bifunctional isocyanate monomer. It further includes a modified form of at least one bifunctional isocyanate monomer selected from the group consisting of:
(14) The polyisocyanate component (A) may further include at least one isocyanate component selected from the group consisting of 2,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and xylene diisocyanate. .
(15) The urethane prepolymer (a) having an isocyanate group is a reaction product of 4,4′-diphenylmethane diisocyanate and a polyol essentially containing a polyether polyol.
(16) 70-100% by mass of a polyether polyurethane polyol having a number average molecular weight of 200 or more and 3000 or less in 100% by mass of the polyol component (B).
(17) The total amount of 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and xylene diisocyanate contained in 100% by mass of the adhesive composition is 10 to 34% by mass. %.

In the laminate of the present invention, the amino-based 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.

  Further, the base material 2 constituting the laminate of the present invention has a metal deposition layer on one surface, and it is preferable that the metal deposition layer is in contact with the adhesive layer.

Further, the present invention provides a laminate comprising, in this order, 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 , 24 hr, 1 atm, 25 ° C.) or less. The present invention relates to a method for producing a laminate, which comprises the following steps (I) to (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% by mass of amino in 100% by mass of solid content of the ink composition. A step of preparing a white ink composition containing a silane coupling agent.
(II-1) After reacting 4,4′-diphenylmethane diisocyanate as an essential component and a polyol as an essential component of a polyether polyol under an isocyanate group excess condition,
At least one bifunctional isomer selected from the group consisting of a trimer of a bifunctional isocyanate monomer, a burette in which water is added to a bifunctional isocyanate monomer, and an adduct in which a monoalcohol is added to a bifunctional isocyanate monomer. A modified isocyanate monomer,
If necessary, at least one isocyanate component selected from the group consisting of 2,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and xylene diisocyanate is mixed,
A urethane prepolymer (a) having an isocyanate group;
4,4′-diphenylmethane diisocyanate;
At least one bifunctional isomer selected from the group consisting of a trimer of a bifunctional isocyanate monomer, a burette in which water is added to a bifunctional isocyanate monomer, and an adduct in which a monoalcohol is added to a bifunctional isocyanate monomer. And a modified isocyanate monomer.
Preparing a polyisocyanate component (A), which can further include at least one isocyanate component selected from the group consisting of 2,4′-diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and xylene diisocyanate;
(II-2) The polyisocyanate component (A) and a polyol component (B) containing 70 to 100% by mass of a polyether polyurethane polyol having a number average molecular weight of 200 to 3000 in 100% by mass of the polyol component (B). Mix
4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and xylene contained in 100% by mass of the total of the polyisocyanate component (A) and the polyol component (B) A step of preparing an adhesive composition having a total amount of diisocyanate of 10 to 34% by 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 laminating 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.

Further, the present invention provides a laminate comprising 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 , 24 hr, 1 atm, 25 ° C.) or less in this order. It relates to another method of manufacturing the body. That is, the present invention relates to a method for producing a laminate including the following steps (I) to (III) and (VII) to (IX).
(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% by mass of amino in 100% by mass of solid content of the ink composition. A step of preparing a white ink composition containing a silane coupling agent.
(II-1) After reacting 4,4′-diphenylmethane diisocyanate as an essential component and a polyol as an essential component of a polyether polyol under an isocyanate group excess condition,
At least one bifunctional isomer selected from the group consisting of a trimer of a bifunctional isocyanate monomer, a burette in which water is added to a bifunctional isocyanate monomer, and an adduct in which a monoalcohol is added to a bifunctional isocyanate monomer. A modified isocyanate monomer,
If necessary, at least one isocyanate component selected from the group consisting of 2,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and xylene diisocyanate is mixed,
A urethane prepolymer (a) having an isocyanate group;
4,4′-diphenylmethane diisocyanate;
At least one bifunctional isomer selected from the group consisting of a trimer of a bifunctional isocyanate monomer, a burette in which water is added to a bifunctional isocyanate monomer, and an adduct in which a monoalcohol is added to a bifunctional isocyanate monomer. And a modified isocyanate monomer.
Preparing a polyisocyanate component (A), which can further include at least one isocyanate component selected from the group consisting of 2,4′-diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and xylene diisocyanate;
(II-2) The polyisocyanate component (A) and a polyol component (B) containing 70 to 100% by mass of a polyether polyurethane polyol having a number average molecular weight of 200 to 3000 in 100% by mass of the polyol component (B). Mix
4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and xylene contained in 100% by mass of the total of the polyisocyanate component (A) and the polyol component (B) A step of preparing an adhesive composition having a total amount of diisocyanate of 10 to 34% by 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 substrate 2 to form a precursor of an adhesive layer.
(VIII) a step of overlaying the white ink layer on a precursor of the adhesive layer.
(IX) A step of curing the precursor of the adhesive layer to form an adhesive layer.

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

The polymer polyol referred to in the present invention is a polymer polyol well-known for gravure inks and flexo inks, and is available in polymerization reactions, condensation reactions, natural products, and the like, and most of them have an average molecular weight of 400 to 10,000. It is.

As the structure of the polymer polyol in the present invention, various known polymer polyols generally used for producing a polyurethane resin can be used, and one kind or two or more kinds may be used in combination.
For example, polymer or copolymer polyether polyols (1) such as methylene oxide, ethylene oxide, propylene oxide, and tetrahydrofuran;
Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 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 Or unsaturated low-molecular-weight polyhydric alcohols such as trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, sorbitol and pentaethritol, and adipic acid , Phthalic acid, isophthalic Polycarboxylic acids such as terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, spearic acid, azelaic acid, sebacic acid, trimellitic acid, pyromellitic acid, or these Polyester polyols (2) obtained by dehydration condensation or polymerization with an anhydride;
Polyester polyols (3) obtained by ring-opening polymerization of cyclic ester compounds, for example, lactones such as polycaprolactone, polyvalerolactone, and poly (β-methyl-γ-valerolactone);
Polycarbonate polyols (4) obtained by reacting the low molecular weight polyhydric alcohols and the like with, for example, dimethyl carbonate, diphenyl carbonate, ethylene carbonate, phosgene and the like;
Polybutadiene glycols (5);
Glycols (6) obtained by adding ethylene oxide or propylene oxide to bisphenol A;
Obtained by copolymerizing one or more hydroxyethyl, hydroxypropyl acrylate, acrylhydroxybutyl and the like, or their corresponding methacrylic acid derivatives in one molecule with, for example, acrylic acid, methacrylic acid or an ester thereof. Acrylic polyol (7).

  Among the polymer polyols, polyester polyols and polyether polyols are preferred from the viewpoint of the adhesion of the ink layer to the transparent substrate 1 and the solubility of the ink composition in the solvent, and the number average molecular weight is 500 to 5,000. Is preferred. Examples of the polyester polyols include diols having one or more branched structures selected from 2-methyl-1,3-propanediol, 2-ethyl-2-butyl-1,3propanediol, 3-methyl-1,5-pentanediol, and the like. A polyester polyol obtained by polymerizing adipic acid has a branched structure, and thus is particularly excellent in adhesion to a substrate and solubility. Particularly, a polyester polyol obtained by polymerizing 3-methyl-1,5 pentanediol and adipic acid is preferable. As the polyether polyols, a propylene oxide polymer having appropriate flexibility in terms of adhesion to a substrate is preferable. More preferably, a polyester polyol having these branched structures and a polyether polyol are used in combination.

Examples of the polyisocyanate compound used in forming the polyurethane polyurea resin include various known aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates 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, Reel diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatomethyl) 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 dimer isocyanate obtained by converting a carboxyl group of dimer acid into an isocyanate group. These diisocyanate compounds can be used alone or in combination 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 when forming the polyurethane polyurea resin is a chain extender for increasing the molecular weight of the urethane prepolymer, and a terminal blocking agent for stopping the reaction of the polyurethane polyurea resin. is there.

Examples of the chain extender include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4′-diamine, and the like. Further, 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-2-hydroxyethylethylenediamine, Use of amines having a hydroxyl group in a molecule such as -2-hydroxyethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, and di-2-hydroxypropylethylenediamine Can be done. These chain extenders can be used alone or as a mixture 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 and the like, 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. Further, monoamine-type amino acids such as glycine, alanine, glutamic acid, taurine, aspartic acid, aminobutyric acid, valine, aminocaproic acid, aminobenzoic acid, aminoisophthalic acid, and sulfamic acid are also included. By using a monoamine having a hydroxyl group such as monoethanolamine, a hydroxyl group can be added to a terminal of the polyurethane polyurea resin.

  Further, as the terminal blocking agent, a monovalent active hydrogen compound can be used in addition to the compound having an amino group described above. Such compounds include, for example, 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 high-molecular polyol and a polyisocyanate compound are reacted with a solvent inert to isocyanate groups as necessary, and further, if necessary, with a catalyst at a temperature of 10 to 100 ° C. To produce a urethane prepolymer having an isocyanate group. Next, the urethane prepolymer is reacted with the compound having an amino group at 10 to 80 ° C.

  The method of the reaction between the urethane prepolymer and the compound having an amino group may be a method in which a solution of the compound having an amino group is gradually dropped into the urethane prepolymer solution, or a method in which the urethane prepolymer solution is added to the solution of the compound having an amino group. The reaction can be carried out by any method in the present invention.

  The mass average molecular weight of the polyurethane polyurea resin in the present invention is 15,000 or more from the viewpoint of the blocking resistance of the obtained ink composition, the pigment can be appropriately dispersed, and the work in the printing process using the obtained ink composition It is preferable to be 70,000 or less from the viewpoint of high efficiency.

The polyurethane polyurea resin in the present invention has a hydroxyl group on the side chain or terminal of the polyurethane polyurea resin, and has a hydroxyl value of 0.1 to 20 mgKOH / g, preferably 1 to 15 mgKOH / g. When the hydroxyl value is 0.1 mgKOH / g or more, a tough ink layer crosslinked with an amino-based silane coupling agent described later can be obtained. Since the components in the adhesive composition described later hardly 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 force of the polyurethane polyurea resin increases, and the components in the adhesive composition hardly penetrate into the ink layer, so that the appearance and physical properties of the laminate are improved.
A method for adding a hydroxyl group to the side chain of the polyurethane polyurea resin includes using the amine having a hydroxyl group as a chain extender. Examples of the method for adding a hydroxyl group to the terminal of the polyurethane polyurea resin include the use of the hydroxyl-containing monoamines as a terminal blocking agent. In the polyurethane polyurea resin of the present invention, a hydroxyl group can be added to the polyurethane polyurea resin by an arbitrary method, but it is preferable that the hydroxyl group is added to both the side chain and the terminal.

Next, the amino-based silane coupling agent contained in the ink composition will be described.
The amino-based silane coupling agent in the present invention refers to a compound having a primary to tertiary amino group and an alkoxysilyl group in one molecule. The alkoxysilyl group in the amino-based silane coupling agent molecule forms a crosslink with the hydroxyl group present on the surface of the polyurethane polyurea resin or the white inorganic pigment in the ink composition, so that the laminated adhesive composition penetrates. A dried or cured product of the tough ink composition, which does not cause any problem, 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 the adhesive) does not penetrate into the ink layer, it does not hinder the curing of the adhesive layer and provides good lamination. Physical properties can be realized.

The ink composition in the present invention contains the amino-based silane coupling agent in an amount of 0.15 to 7% by mass, preferably 0.5 to 3% by mass, based on 100% by mass of the solid content of the ink composition. . When the content of the amino-based silane coupling agent is 0.15% by mass or more, the ink layer can be sufficiently crosslinked, and the appearance and physical properties of the laminate can be improved.
When the content of the amino-based silane coupling agent is 7% by mass or less, the appearance and physical properties of the laminate can be improved. The reason is considered as follows. The amino-based silane coupling agent in the ink layer also reacts with the polyisocyanate component (A) in the adhesive or forms a basic compound during the curing reaction between the polyisocyanate component (A) and the polyol (B) in the adhesive. It also acts as a catalyst. Since the amino group has a higher reactivity with the isocyanate group than the hydroxyl group, the polyisocyanate component (A) is more highly soluble than the polyol (B) if the ink layer contains an excessive amino silane coupling agent. Also reacts preferentially with the amino-based silane coupling agent in the ink layer, and the reaction of the polyisocyanate component (A) in the adhesive layer during curing with the polyol (B) becomes insufficient. Poor body adhesion. On the other hand, if the curing reaction between the polyisocyanate component (A) and the polyol (B) is accelerated by the excess amino silane coupling agent in the ink layer, the viscosity of the adhesive layer during curing increases. As a result, the adhesive layer in the middle of curing cannot spread uniformly on the ink layer, and the appearance of the laminate is inferior.

  The amino-based silane coupling agent in the present invention preferably has a primary amino group. By having a primary amino group, the hydrolysis reactivity and condensation reactivity of alkoxy groups in the same molecule are superior, and an efficient cross-linking structure is formed in the ink composition. Can be suppressed, and the appearance of the laminate becomes good. Such compounds include, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, and the like.

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

Further, 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 lower hydrolysis and condensation reactivity of alkoxy groups than primary amino groups, but the presence of four or more alkoxy groups allows efficient crosslinking with one molecule. Since the structure can be formed, the appearance of the laminate is improved as well as an amino-based silane coupling agent having a primary amino group. Such compounds include, for example, bis (3-trimethoxysilylpropyl) amine, bis (3-
Triethoxysilylpropyl) amine, bis (3-methyldimethoxysilylpropyl) amine, bis (triethoxysilylmethyl) amine, N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine and the like.

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

  In particular, the white inorganic pigment is preferably titanium oxide. Since titanium oxide has excellent chemical resistance, it can suppress penetration of the adhesive composition into the white ink layer, and can provide a laminate having a good appearance in terms of coloring power and hiding power. Further, from the viewpoint of the crosslinking action between the titanium oxide surface and the amino-based silane coupling agent, it is suitable for obtaining a laminate having both physical properties and appearance.

  Various resins other than the polyurethane polyurea resin can be used in combination in the ink composition of the present invention, depending on the application and the base material. Examples of resins used include polyurethane polyurea resins other than those described above, polyurethane resins, vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinyl acetate copolymers, vinyl chloride-acrylate copolymers, and chlorinated polypropylene resins. , 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 resin, terpene resin, phenol modified Examples include terpene resins, ketone resins, cyclized rubbers, chlorinated rubbers, butyral, petroleum resins, and modified resins thereof. Particularly, vinyl chloride-vinyl acetate copolymer is preferable. These resins can be used alone or in combination of two or more, and the content thereof is preferably 0.5 to 20% by mass based on 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 ester solvents such as methyl acetate, ethyl acetate, normal propyl acetate, isopropyl acetate, isobutyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and methanol. Known solvents such as alcohol solvents such as ethanol, normal propanol, isopropyl alcohol, normal butanol, propylene glycol monoethyl ether and propylene glycol monomethyl ether, and hydrocarbon solvents such as methylcyclohexane and ethylcyclohexane can be used. In recent years, from the viewpoint of the working environment, 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. In the ink composition of the present invention, even a solvent excluding this is preferably used. Can be

  The ink composition of the present invention can be produced by dissolving and / or dispersing a resin, a pigment and the like in an organic solvent. More specifically, a pigment dispersion is prepared by dispersing a white inorganic pigment in a polyurethane polyurea resin and other resins, and further, if necessary, other compounds in an organic solvent. An ink composition can be produced by blending a resin, another resin, an organic solvent, and if necessary, other compounds. The above step of obtaining the pigment dispersion is also referred to as a meat cutting step.

  The method for incorporating the amino-based silane coupling agent into the ink composition may be a general method for incorporating an additive into the ink composition, and is not particularly limited. For example, (1) a pigment is previously treated with an amino-based silane coupling agent by a dry or wet method; (2) an amino-based silane coupling agent is added all at once when the pigment is kneaded; There is a method of adding an amino-based silane coupling agent after meat, (4) adding to an ink just before printing, and the like.

  In order to stably disperse the pigment in the organic solvent, a dispersant may be used in combination to further stably disperse the pigment. As the dispersant, an anionic, nonionic, cationic, amphoteric or other surfactant 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 storage stability of the ink and 5% by mass or less from the viewpoint of lamination suitability. More preferably, 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 pulverization medium of the disperser, the filling rate of the pulverization medium, 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, a roller mill, a ball mill, a pebble mill, an attritor, a sand mill and the like can be used.

  When bubbles or unexpectedly large particles are included in the ink composition, it is preferable to remove the ink composition by filtration or the like in order to reduce the quality of the printed matter. A conventionally 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 sedimentation of the pigment and dispersing the pigment appropriately, and is 1000 mPa · s or less from the viewpoint of work efficiency during ink composition production or printing. It is preferably within the range. The viscosity is a viscosity measured at 25 ° C. with a Tokimec B-type viscometer.

Next, the adhesive layer constituting the laminate of the present invention will be described. 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 according to the present invention will be described.
Hereinafter, 4,4'-diphenylmethane diisocyanate is 4,4'-MDI,
2,4'-diphenylmethane diisocyanate is converted to 2,4'-MDI,
TDI for tolylene diisocyanate, XDI for xylylene diisocyanate,
Hexamethylene diisocyanate as HDI, isophorone diisocyanate as IPDI
Sometimes abbreviated.

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

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

The polyol for forming the urethane prepolymer (a) will be described.
The polyol contains a polyether polyol as an essential component, and can further contain a polyester polyol. Polyether polyols generally have lower viscosities in the molten state than polyester polyols. Therefore, polyols used in forming a urethane prepolymer in the polyisocyanate component (A), which is a component of the solventless adhesive composition, It is important that the polyether polyol is essential. Further, by using a polyester polyol in combination, it is possible to increase the compatibility with the polyol component (B) described later and also increase the cohesive force of the adhesive layer.
When a polyester polyol is used in combination, the content is preferably 50% by mass or less based on the viscosity of the adhesive composition in 100% by mass of the polyol.

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

As the polyether polyol, trifunctional or higher polyfunctional ones can be used in addition to bifunctional ones. Further, a plurality of compounds having different numbers of functional groups can be used in combination.
The polyether polyol preferably has a number average molecular weight of 100 or more and 5000 or less. Further, a plurality of compounds having different molecular weights can be used in combination.

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

  Examples of the low molecular weight diol include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3′-dimethylolheptane, Low molecular diols such as 2-methyl-1,3-propanediol and the like, and mixtures thereof are exemplified.

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

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

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

The polyisocyanate component (A) used in the present invention preferably contains an isocyanate group in an amount of 10% by mass or more and less than 21% by mass.
When the isocyanate group content of the polyisocyanate component (A) is within the above range, a laminate having better appearance can be formed when a film substrate having high gas barrier properties is used. The content (% by mass) of the isocyanate group is determined by titration with hydrochloric acid as described later.

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

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

The polyether polyol which is an essential raw material of the polyether polyurethane polyol will be described. Examples of the polyether polyol include polyether diol and polyether triol.
Examples of the polyether diol include, for example, a polyether diol obtained by polymerizing an oxirane compound such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran with a bifunctional low-molecular-weight polyol such as water, ethylene glycol, and propylene glycol as an initiator. Ether diols.
Examples of the polyether triol include, for example, polyether triol obtained by polymerizing an oxirane compound such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran with a small amount of triol such as trimethylolpropane or glycerin as an initiator. .

The polyol component (B) may contain other polyol components such as a polyester polyol in addition to the polyether polyurethane polyol, as long as the object of the present invention is not impaired.
Examples of the polyester polyol include, for example, terephthalic acid, isophthalic acid, adipic acid, azelaic acid, polyvalent carboxylic acids such as sebacic acid or their dialkyl esters 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, glycols such as polyoxyethylene glycol, polyoxypropylene glycol, and polytetramethylene ether glycol Polyols or lactones such as polycaprolactone, polyvalerolactone, poly (β-methyl-γ-valerolactone) obtained by reacting the same with a mixture thereof or a mixture thereof. Polyester polyols obtained by ring-opening polymerization.
In addition, vegetable oils such as castor oil and polyester compounds derived from vegetable oils can also be used.

  Typical vegetable oils are hemp seed oil, linseed oil, eno oil, deer 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, soybean 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, coconut oil, peanut oil, dehydrated castor oil and the like.

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

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

  Examples of the polyether ester polyol include, for example, terephthalic acid, isophthalic acid, adipic acid, azelaic acid, dibasic acids such as sebacic acid or a dialkyl ester thereof, or a mixture thereof, and a polyether diol obtained by reacting the polyether diol. Ether ester diols may be mentioned.

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

  Examples of acrylic diols include hydroxyethyl acrylate, hydroxypropyl acrylate, acrylhydroxybutyl and the like containing one or more hydroxyl groups in one molecule, or their corresponding methacrylic acid derivatives and the like, for example, acrylic acid and methacrylic acid. It is obtained by copolymerizing an acid or an ester thereof.

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

  Examples of the low molecular triol include low molecular triols such as castor oil, trimethylolpropane, and glycerin, and mixtures thereof. Of these, low molecular weight triols and polyether triols are preferred from the viewpoint of reactivity.

In the adhesive composition of the present invention, when the number of moles 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 mol or more and 400 mol or less. Is preferred.
When the number of moles of hydroxyl groups in the polyol component (B) is set to 100 moles, since the number of moles of isocyanate groups in the polyisocyanate component (A) is within the above range, good aging under high humidity can be achieved. Adhesive strength can be exhibited.

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

The adhesive composition of the present invention can further contain particles having an average particle diameter of 1 × 10 ⁻⁴ mm or more and 4 × 10 ⁻⁴ mm or less. By containing particles having an average particle diameter within the above range, a laminate having a more external appearance can be obtained when a film substrate having high gas barrier properties is used and applied and bonded at high speed. If the particles are too small, the flow properties will not change much when 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.

  Either an inorganic compound or an organic compound can be used as such particles, and they may be used alone or in combination of two or more.

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

  Examples of the organic compound particles include, for example, benzoguanamine resin, silicone resin, styrene resin, crosslinked polystyrene, epoxy resin, phenol resin, fluororesin, polyethylene resin, polyester resin, polyimide resin, polyamide resin, polyacetal resin, polyurethane resin, acetic acid Powders of vinyl copolymer resin, polyphenylene oxide resin, nylon 6, nylon 12, cellulose, acrylic resin, methacrylic resin and the like can be given. Among these, benzoguanamine resin is awarded.

The content of the particles is as follows: particles having an average particle diameter of 1 × 10 ⁻⁴ mm or more to 4 × 10 ⁻⁴ mm or less with respect to a total of 100 parts by mass of the polyisocyanate component (A) and the polyol component (B). Preferably, C) is contained in an amount of 0.01 to 10 parts by mass.
By being in the above range, the appearance and the adhesive strength can be improved in a well-balanced manner.

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

The adhesive composition of 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, the temperature is 25 ° C or higher and 80 ° C or lower. It is preferable to mix them. 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 obtained 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 secure good workability. If the coating temperature is 60 ° C. or lower, a good coating appearance may not be obtained. There is.
On the other hand, if the melt viscosity at 60 ° C. is less than 50 mPa · s, sufficient adhesive performance cannot be obtained due to a low initial cohesive force, or the thickness of the coating film is uniform when the adhesive composition is applied to the substrate. This tends to cause poor appearance and warpage.

The adhesive composition of the present invention further requires additives such as an antioxidant, an ultraviolet absorber, a hydrolysis inhibitor, an antioxidant, a thickener, a plasticizer, an antifoaming agent, a pigment, and a filler. Can be used accordingly.
Further, in order to further enhance the adhesion performance, an adhesion aid such as a silane coupling agent, phosphoric acid, a phosphoric acid derivative, an acid anhydride, and a tacky resin can be used. 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, chlorosilanes such as vinyltrichlorosilane, aminosilanes such as N- (dimethoxymethylsilylpropyl) ethylenediamine, N- (triethoxysilylpropyl) ethylenediamine, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxy Epoxy silanes such as silane and vinyl silanes such as vinyl triethoxy silane are exemplified.
The addition amount of the silane coupling agent is preferably from 0.1 to 5% by mass based on the entire adhesive composition.

  Among the phosphorus oxyacids or derivatives thereof used in the present invention, the phosphorus oxyacid may be any one having at least one free oxyacid, for example, hypophosphorous acid, 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 are exemplified. Examples of the phosphorus oxyacid derivative include those obtained by partially esterifying the above-described phosphorus oxyacid with alcohols while leaving at least one free oxyacid. 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 phloroglicinol. The oxyacid of phosphorus or a derivative thereof may be used alone or in combination of two or more. The addition amount of the oxygen acid of phosphorus or a derivative thereof is 0.01 to 10% by mass, preferably 0.05 to 5% by mass, and more preferably 0.1 to 1% by mass, based on the whole composition.

The laminate of the present invention and a method for producing the same will be described.
As described above, the laminate of the present invention has the transparent substrate 1, the white ink layer, the adhesive layer, and the substrate 2 in this order.

  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-based resins such as polystyrene, AS resin and ABS resin, nylon, polyamide, and polystyrene. Vinyl chloride, polyvinylidene chloride, cellophane, paper, aluminum, etc., or in the form of a film or sheet made of a composite material of these, applied using the above printing method, dried or cured by drying in an oven By fixing, a printed matter can be obtained. The base material may be subjected to a vapor coating treatment and / or a coating treatment such as polyvinyl alcohol on the surface with a metal oxide or the like, and may be further subjected to a surface treatment such as a corona treatment.

The white ink layer is a dried or cured product of the above-described white ink composition containing a polyurethane polyurea resin having a specific hydroxyl group and a specific amount of an amino-based 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 composition. The white ink composition can be printed by a known printing method such as gravure printing or flexographic printing, but it is particularly preferable to print by a gravure printing method. As the cylinder used for gravure printing, a known cylinder such as an engraving type or a corrosion type is 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 in a mixture, and after printing, passes through an oven, and is dried or cured to obtain a white ink. A layer is formed. The temperature of the oven is usually 40 to 80C, and the printing speed is usually 50 to 300 m / min. In winter, when the printing environment is low, in order to ensure that the crosslinking reaction by the amino-based silane coupling agent proceeds and cure the ink composition, the adhesive composition is applied on the white ink layer after 12 hours or more from printing. It is preferable to apply the coating or to overlap the white ink layer and the precursor of the adhesive layer. White ink layer is usually 0.5 to 5 g / ^{m 2,} it is preferable that 1~3.5g / ^{m 2.}

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) as described above. , 4,4′-MDI, 2,4′-MDI, TDI, HDI, and IPDI are cured products of the adhesive composition mixed so as to be 10 to 34% by mass. Can be obtained in a way.
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 hr, 1 atm, 25 ° C.) or less, and a precursor of the adhesive layer is formed. Form. The amount of the adhesive composition applied is appropriately selected depending on the type of the base material 2 and the coating conditions, but is usually 1 to 5 g / m ² , preferably 1.5 to 4.5 g / m 2. ² .
Thereafter, a substrate 2 having an oxygen permeability of 100 CC (m ² , 24 hr, 1 atm, 25 ° C.) or less is laminated on the precursor of the adhesive layer, or a white ink layer, that is, a transparent substrate 1 is formed on the precursor of the adhesive layer. After laminating the surface of the white ink layer provided above on which the transparent substrate 1 is not in contact, the precursor is cured by aging at room temperature or under heating, and the precursor is cured to form an adhesive layer. Manufacture the body. In the case of the adhesive composition of the present invention, the time required for aging is about one day. Moreover, in the case of the adhesive composition of the present invention, sufficient adhesive performance can be exhibited even when the environmental humidity during coating to aging is high.

The substrate 2 used has an oxygen permeability of 100 CC (m ² , 24 hr, 1 atm, 25 ° C.) or less. Oxygen permeability is affected by thickness. In the present application, a substrate having 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) per unit thickness (1 μm) and the thickness.
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, so that it 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 has a thickness of 4 μm or more.
Nylon 6 having an oxygen permeability coefficient of 1700 CC has a thickness of 17 μm or more.
Nylon 66 having an oxygen permeability coefficient of 1,925 CC has a thickness of not less than 19.25 μm.
Polyethylene terephthalate having an oxygen permeability coefficient of 768 CC has a thickness of 7.68 μm or more.
The terephthalic acid-bisphenol copolymer polyarylate having an oxygen permeability coefficient of 2580 CC has a thickness of 25.8 μm or more.
A polyacetal having an oxygen permeability coefficient of 4850 CC can be obtained by adjusting the film thickness to 48.5 μm or more.
Polychlorotrifluoroethylene having an oxygen permeability coefficient of 650 CC has a thickness of 6.5 μm or more.
Polyvinylidene fluoride having an oxygen permeability coefficient of 1300 CC can be used as the base material 2 if the film thickness is 13 μm or more.

A vapor-deposited film obtained by vapor-depositing aluminum, silicon oxide, aluminum oxide, or the like on various plastic films can also be used as the base material 2. In many cases, the thickness of the vapor-deposited layer is about 1 to 500 nm, and by providing such a vapor-deposited 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 deposition layer has an oxygen permeability of 20 to 10 CC (m ² , 24 hr, 1 atm, 25 ° C.),
A polyethylene terephthalate film provided with an aluminum vapor-deposited layer has an oxygen permeability of ² to 0.3 CC (m ² , 24 hr, 1 atm, 25 ° C.),
A polyethylene terephthalate film provided with a vapor-deposited layer of aluminum oxide has an oxygen permeability of 4 to 0.5 CC (m ² , 24 hr, 1 atm, 25 ° C.),
A polyethylene terephthalate film provided with a silicon oxide deposition layer has an oxygen permeability of 5 to 0.3 CC (m ² , 24 hr, 1 atm, 25 ° C.), and is used as the substrate 2.
The metal foil of stainless steel, iron, copper, lead or the like has an oxygen permeability of 0 CC (m ² , 24 hr, 1 atm, 25 ° C.) regardless of the thickness.
As the base material 2, a material in which a vapor deposition layer is provided on various plastic films or a metal foil is preferable, and a material in which metal is vapor-deposited on various plastic films (hereinafter, also referred to as a vapor deposition film) is preferable. Then, the metal deposition layer is preferably in contact with the adhesive layer.

The oxygen permeability can be determined using an oxygen permeability measuring device according to JIS K 7126.
For example, Hitachi High-Technologies Corporation MОCОN oxygen permeability measurement device (ОX-TR
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 using a carrier gas (nitrogen). Convert.

  Hereinafter, the present invention will be described more specifically with reference to examples. All percentages and parts in Examples and Comparative Examples are based on mass unless otherwise specified.

<Methods for measuring mass average molecular weight (Mw) and number average molecular weight (Mn)>
For measurement of the mass average molecular weight (Mw) and the number average molecular weight (Mn), Showa Denko GPC (gel permeation chromatography) "Shodex GPC System-21" was used. GPC is liquid chromatography in which substances dissolved in a solvent are separated and quantified based on the difference in molecular size. Tetrohydrofuran is used as a solvent, and the molecular weight is determined in terms of polystyrene.

<Method for measuring hydroxyl value>
About 1 g of the sample was precisely weighed and placed in a stoppered Erlenmeyer flask, and dissolved by adding 100 ml of a mixed solution of toluene / ethanol (volume ratio: toluene / ethanol = 2/1). Further, exactly 5 ml of an acetylating agent (a solution in which 25 g of acetic anhydride was dissolved in pyridine to make the volume 100 ml) was added, and the mixture was stirred for about 1 hour. To this, phenolphthalein TS 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 red.
The hydroxyl value was determined by the following (Equation 2). The hydroxyl value was a value in a dry state of the resin (unit: mgKOH / g).
(Equation 1) Hydroxyl value (mgKOH / g) = [{(ba) × F × 28.25} / S] / (nonvolatile content / 100) + D
Here, S: sampled amount (g)
a: consumption of 0.1N alcoholic potassium hydroxide solution (ml)
b: consumption of 0.1N alcoholic potassium hydroxide solution in blank experiment (ml)
F: titer of 0.1N alcoholic potassium hydroxide solution
D: Acid value (mgKOH / g)

<Method of measuring acid value>
About 1 g of the sample was precisely weighed and placed 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, phenolphthalein TS was added as an indicator, and after holding for 30 seconds, titration was performed with a 0.1N alcoholic potassium hydroxide solution until the solution turned red. The acid value was determined by the following (Equation 3). The acid value was a value in the dry state of the resin (unit: mgKOH / g).
(Equation 2) Acid value (mgKOH / g) = {(5.611 × a × F) / S} / (nonvolatile content / 100)
Here, S: sampled amount (g)
a: consumption of 0.1N alcoholic potassium hydroxide solution (ml)
F: titer of 0.1N alcoholic potassium hydroxide solution

<Method of 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 thereto and dissolved. To this, phenolphthalein TS was added as an indicator, and after holding for 30 seconds, titration was performed with a 0.25N hydrochloric acid solution until the solution turned reddish. NCO (% by mass) was determined by the following (Equation 4).
(Equation 3) NCO (% by 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 of 0.25N hydrochloric acid solution in blank experiment
F: titer of 0.25N hydrochloric acid solution

(Synthesis of polyurethane polyurea resin for ink composition)
[Synthesis Example 1-1]
In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet tube, a polyester polyol A1 (Kuraray polyol P-2010, a copolymer of 3-methyl-1,5-pentanediol and adipic acid, 11.36 parts of polyether polyol B (EXCENOL 2020, polymer of propylene oxide, number average molecular weight 2000, manufactured by Asahi Glass) 11.36 parts of polyether polyol B (average molecular weight 2000, manufactured by Kuraray Co., Ltd.), 5.05 of isophorone diisocyanate (hereinafter also abbreviated as IPDI) Parts, 4.36 parts of ethyl acetate, and 0.003 parts of tin 2-ethylhexanoate, and reacted at 90 ° C. for 5 hours under a nitrogen stream.
A solution of a urethane prepolymer having an isocyanate group at a terminal was obtained.
Then, 1.92 parts of isophoronediamine (hereinafter 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 abbreviated as IPA) 28 The resulting urethane prepolymer solution was slowly added at room temperature to the mixture of the above components, and then reacted at 50 ° C. for 1 hour. The solid content was 30%, the weight average molecular weight was 50,000, and the hydroxyl value was 0.1 mg KOH / resin. 1 g of a polyurethane polyurea resin solution (PU1) was obtained.
In this synthesis example, a solution of the urethane prepolymer obtained in the amines was dropped, and a chain extension reaction was performed.

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

[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, and isophorone diisocyanate (hereinafter abbreviated as IPDI). 5.19 parts, 4.36 parts of ethyl acetate and 0.003 parts of tin 2-ethylhexanoate were charged, reacted at 90 ° C. for 5 hours under a nitrogen stream, added with 7.5 parts of ethyl acetate, cooled, and cooled. A solution of a urethane prepolymer having an isocyanate group was obtained.
Then, 1.23 parts of isophoronediamine (hereinafter abbreviated as IPDA), 0.16 parts of 2-hydroxyethylethylenediamine, 0.07 parts of monoethanolamine, 30.147 parts of ethyl acetate, and A mixture of 28 parts of isopropyl alcohol (hereinafter abbreviated as IPA) is gradually added at room temperature, and then reacted at 50 ° C. for 1 hour. A polyurea resin solution (PU5) was obtained.
In this synthesis example, amines were added dropwise to the obtained urethane prepolymer solution to carry out a chain extension reaction.

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

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

[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 charging ratio shown in Table 2.

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

[Production Examples 1-2 to 1-12], [Production Examples 1-14 to 20]
At the charging ratios in Tables 3 and 4, ink compositions (i-2 to i-12, i-14 to i-20) were obtained in the same manner as in Production Example 1-1. The amino-based silane coupling agent and the isocyanate-based curing agent 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 (isocyanate curing agent, manufactured by Toyo Ink)

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

Synthesis of Polyisocyanate Component (α) for Adhesive Composition (Synthesis Example 101)
129 parts of polypropylene glycol having a number average molecular weight of about 400 (hereinafter, referred to as PPG-400), 1018 parts of polypropylene glycol having a number average molecular weight of about 2,000 (hereinafter, referred to as PPG-2000), and about 400 of a number average molecular weight obtained by adding polypropylene glycol to glycerin. Of a triol (hereinafter, referred to as PPG-400-3 function) and 670 parts of 4,4′-MDI were charged into a reaction vessel and heated at 70 ° C. to 80 ° C. for 3 hours while stirring under a nitrogen gas stream to urethanize. The reaction was performed to obtain a polyisocyanate composition α- (1) containing the polyurethane polyisocyanate (a) and unreacted 4,4-diphenylmethane diisocyanate.
The composition α- (1) had an isocyanate group content of 6.9% and an MDI monomer content of 23%.

(Synthesis example 102)
477 parts of adipic acid (hereinafter referred to as ADA) and 323 parts of propylene glycol were charged into a reaction vessel, and the mixture was heated to 150 ° C. to 240 ° C. while stirring under a stream of nitrogen gas to perform an esterification reaction. When the acid value reached 1.3 (mgKOH / g), the reaction temperature was raised 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 obtain an acid value of 0.3 (mgKOH / g). ), A hydroxyl value of 56.1 (mg KOH / g) and a number average molecular weight of about 2,000 to obtain polyester diol 1 having hydroxyl groups at both ends.
222 parts of the obtained polyester diol 1, 112 parts of PPG-400, 666 parts of PPG-2000, 72 parts of PPG-400-3 function, 800 parts of 4,4′-MDI were charged into a reaction vessel, and nitrogen was charged. The mixture was heated at 70 ° C. to 80 ° C. for 3 hours while stirring under a gas stream to perform a urethanization reaction, and a polyisocyanate composition α- () containing polyurethane polyisocyanate (a) and unreacted 4,4-diphenylmethane diisocyanate 2) was obtained.
The composition α- (2) had an isocyanate group content of 10.3% and an MDI monomer content of 28%.

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

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

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

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

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

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

(Formulation Example 404)
Adipic acid: 208 parts and diethylene glycol: 192 parts were charged into a reaction vessel and heated to 150 ° C. to 240 ° C. while stirring under a nitrogen gas stream to perform an esterification reaction. When the acid value became 1.3 (mgKOH / g), the reaction temperature was raised 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, and the acid value was 0.5 (mgKOH / g). ), A hydroxyl value of 56.1 (mg KOH / g) and a number average molecular weight of about 2000 to obtain polyester diol 2 having hydroxyl groups at both ends.
70 parts of the polyether polyurethane polyol b1- (1) obtained in Synthesis Example 201 and 2:30 parts of the polyester diol were mixed to obtain a polyol component B- (4).

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

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

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

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

[Examples 1 to 13], [Comparative Examples 1 to 7]
[Preparation of printed matter]
The ink compositions i-1 to i-20 obtained in Production Examples 1 to 20 were not corona-treated 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 depth of 30 μm. It was printed on a stretched polypropylene film (Toyobo PP film P2102 # 20) and dried or cured by passing through a 60 ° C. oven to form an ink layer on the PP film.

[Production of laminated body]
Using a solventless test coater, the solventless adhesive composition AD2 obtained in Production Example 501 was applied to the surface of the ink layer printed on the PP film at a temperature of 60 ° C and a coating speed of 200 m / min. (Coating amount: 2 g / m ² ), and an aluminum vapor-deposited unstretched polypropylene film having an oxygen permeability of 20 CC (m ² , 24 h, 1 atm, 25 ° C.) (hereinafter referred to as VMCPP; thickness: 25 μm). Were stacked to obtain a laminate (pre-laminate) in a preparation stage.
These pre-laminates were aged in an environment of 25 ° C. and 80% RH for one day to cure the adhesive layer, thereby producing a laminate. With respect to the obtained laminate, the adhesive strength of the laminate and the interface state of the laminate were evaluated according to the following methods. Table 11 shows the results.

(Adhesive strength)
The laminate was cut into a length of 300 mm and a width of 15 mm to obtain a test piece. Using an Instron tensile tester, the film was pulled at a peeling speed of 300 mm / min in an environment of 25 ° C., and the T-shaped peeling strength (N) between ΔPP / VMCPP was measured at a width of 15 mm. This test was performed five times, and the average was determined 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

(Interface state of laminate)
The deposited portion 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 citron skin-like pattern or small spot-like pattern is observed in the deposited portion.
4: A small spot-like pattern is not observed in the vapor deposition portion, but a little yuzu skin-like pattern is observed. There is no problem in use.
3: A small spot-like pattern is not observed in the vapor deposition portion, but a lot of yuzu skin-like patterns are observed. There is no problem in use.
2: Not only a yuzu skin-like pattern but also a small spot-like pattern is slightly observed on the deposition surface.
1: Many small spot-like patterns as well as yuzu skin-like patterns are observed on the deposition surface.

As shown in Table 10, a hydroxyl group contained a polyurethane polyurea resin having a concentration of 0.1 to 20 (mg KOH / g), and an amino silane coupling agent was added in an amount of 0.15 to 7 in a solid content of 100% by mass of the ink composition. In Examples 1 to 13 using a white ink composition containing 1% 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 was used. The permeation of the isocyanate monomer can be suppressed. As a result, as compared with Comparative Examples 1 to 6, the appearance and adhesion after aging at 25 ° C. for 1 day are excellent.
Comparative Example 1 uses an ink composition containing a polyurethane polyurea resin having a hydroxyl value of 21 mgKOH / g, so that the cohesive force of the ink layer is poor and the isocyanate monomer such as 4,4′-MDI in the adhesive composition is used. Penetration cannot be prevented, resulting in poor appearance.
In Comparative Example 2, since an ink composition containing a polyurethane polyurea resin having a hydroxyl group of 0 mgKOH / g was used, crosslinking with an amino-based silane coupling agent could not be performed, and the appearance was poor.
In Comparative Example 3, since the amino-based silane coupling agent contained only 0.1% by mass in 100% by mass of the solid content of the ink composition, the crosslinking by the coupling agent was insufficient and the appearance was not improved.
In Comparative Example 4, since the amino-based silane coupling agent was also contained in excess (7.8% by mass based on 100% by mass of the solid content of the ink composition), the amino-based coupling agent and the adhesive which did not participate in crosslinking were used. The reaction between the hydroxyl group component and the isocyanate component in the adhesive becomes insufficient due to the reaction with the isocyanate component, and the laminate strength of the laminate decreases. In addition, the amino-based silane coupling agent transferred to the adhesive layer promotes the reaction of the adhesive as a basic catalyst, so that the adhesive leveling property during the curing of the adhesive is reduced, so that the appearance is not sufficient. .
Comparative Example 5 was poor in appearance because no amino-based silane coupling agent was added.
In Comparative Example 6, not an amino-based silane coupling agent but an alkyl-based silane coupling agent was added, and it was confirmed that the appearance was not improved.
In Comparative Example 7, an isocyanate-based curing agent was added to the ink, and the appearance was poor even when the isocyanate-based curing agent was added. Probably, the amino-based silane coupling agent has two kinds of functional groups, an amino group and a silanol group, and can react not only with both the polyurethane polyurea resin and the pigment, but also by reacting the silanol group with the pigment. Is oriented to the outside of the pigment, the affinity with the polyurethane polyurea resin is improved, and the pigment is uniformly dispersed, so that it is possible to uniformly and uniformly crosslink between the binder and the pigment. .

[Examples 14 to 22] [Comparative Examples 8 to 13]
As shown in Table 11, i-3 was used in place of the ink composition i-1, and the solvent-free adhesive composition AD1 obtained in Production Examples 501 and 503 to 516 was used instead of the adhesive composition AD2. A laminate was obtained in the same manner as in Example 1 except that Sample Nos. 3 to 16 were used, and evaluated in the same manner. Table 11 shows the results.

As shown in Table 11, it can be seen that Examples 14 to 22 in which an adhesive layer was formed with the adhesive composition of the present invention had excellent appearance and adhesive strength after aging at 25 ° C for 1 day.
In contrast, Comparative Example 8 did not use 4,4′-MDI for the urethane prepolymer,
Since only 2,4-MDI is used, the reaction rate is too slow and the adhesive strength after aging at 25 ° C. for 1 day is not sufficient.
In Comparative Example 9, the polyether polyurethane polyol b1- (3) having a weight average molecular weight of 3200 was used as the polyol component (B) as the polyol component B- (5), so that the smoothness during coating was reduced and the appearance was poor. Becomes
Comparative Example 10 used tripropylene glycol having a weight average molecular weight of 191 as the polyol component (B) as the polyol B- (6), so the reaction rate with the isocyanate component (A) was too high, and the adhesive in the middle of curing was used. The appearance is not sufficient because the leveling of the layer is reduced.
Comparative Example 11 uses 40% of a polyester polyol as the polyol component (B), so that the compatibility between the polyol component (B) and the polyisocyanate component (A) is reduced, so that the appearance is reduced.
Comparative Example 12 contains 34.2% of the isocyanate monomer after blending, so that the permeation of the isocyanate component into the ink occurs, and the appearance of the laminate after coating is not sufficient.
In Comparative Example 13, since the isocyanate monomer was contained in the adhesive after compounding in an amount of 34.2%, the appearance of the laminate after coating was not sufficient due to the penetration of the isocyanate component into the ink.

[Examples 23 to 34] [Comparative Examples 14 to 20]
As shown in Table 12, a laminate was obtained in the same manner as in Example 1 except that the solvent-free adhesive composition AD8 obtained in Production Example 508 was used instead of the adhesive composition AD2. , And were evaluated in the same manner. Table 13 shows the results.

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

Claims (8)

A laminate comprising, 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 , 24 hr, 1 atm, 25 ° C.) or less,
A laminate that satisfies all of the following conditions (1) to (3) for the white ink layer and the following conditions (11) to (17) for the adhesive layer:
(1) The white ink layer is a dried or cured white ink composition containing a polyurethane polyurea resin, a white inorganic pigment, an amino-based silane coupling agent, and an organic solvent.
(2) The hydroxyl group of the polyurethane polyurea resin is 0.1 to 20 (mgKOH / g).
(3) The amino-based silane coupling agent is contained in an amount of 0.15 to 7% by mass based on 100% by mass of the solid content of the 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) contains a urethane prepolymer (a) having an isocyanate group and 4,4′-diphenylmethane diisocyanate.
(13) The polyisocyanate component (A) is composed of a trimer of a bifunctional isocyanate monomer, a burette in which water is added to a difunctional isocyanate monomer, and an adduct in which a monoalcohol is added to a bifunctional isocyanate monomer. It further includes a modified form of at least one bifunctional isocyanate monomer selected from the group consisting of:
(14) The polyisocyanate component (A) may further include at least one isocyanate component selected from the group consisting of 2,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and xylene diisocyanate. .
(15) The urethane prepolymer (a) having an isocyanate group is a reaction product of 4,4′-diphenylmethane diisocyanate and a polyol essentially containing a polyether polyol.
(16) 70-100% by mass of a polyether polyurethane polyol having a number average molecular weight of 200 or more and 3000 or less in 100% by mass of the polyol component (B).
(17) The total amount of 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and xylene diisocyanate contained in 100% by mass of the adhesive composition is 10 to 34% 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 laminate according to claim 2, wherein the silane coupling agent having a primary amino group among the amino silane coupling agents further has a secondary amino group.   The laminate according to any one of claims 1 to 3, wherein the modified bifunctional isocyanate monomer contained in the polyisocyanate component (A) is a modified hexamethylene diisocyanate.   The laminate according to claim 4, wherein the modified hexamethylene diisocyanate is a trimer of hexamethylene diisocyanate or a burette obtained by adding water to hexamethylene diisocyanate.   The laminate according to any one of claims 1 to 4, wherein the base material (2) has a metal deposition layer on one surface, and the metal deposition layer is in contact with an adhesive layer. A method for producing a laminate comprising a transparent substrate 1, a white ink layer, an adhesive layer, and a substrate 2 having an oxygen permeability of 100 cc (m ² , 24 hr, 1 atm, 25 ° C.) or less in this order, A method for producing a laminate comprising the following steps (I) to (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% by mass of amino in 100% by mass of solid content of the ink composition. A step of preparing a white ink composition containing a silane coupling agent.
(II-1) After reacting 4,4′-diphenylmethane diisocyanate with a polyol essentially comprising a polyether polyol under conditions of an excess of isocyanate groups,
At least one bifunctional isomer selected from the group consisting of a trimer of a bifunctional isocyanate monomer, a burette in which water is added to a bifunctional isocyanate monomer, and an adduct in which a monoalcohol is added to a bifunctional isocyanate monomer. A modified isocyanate monomer,
If necessary, at least one isocyanate component selected from the group consisting of 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and xylene diisocyanate,
A urethane prepolymer (a) having an isocyanate group;
4,4′-diphenylmethane diisocyanate;
At least one bifunctional isomer selected from the group consisting of a trimer of a bifunctional isocyanate monomer, a burette in which water is added to a bifunctional isocyanate monomer, and an adduct in which a monoalcohol is added to a bifunctional isocyanate monomer. And a modified isocyanate monomer.
Preparing a polyisocyanate component (A), which can further include at least one isocyanate component selected from the group consisting of 2,4′-diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and xylene diisocyanate;
(II-2) mixing the polyisocyanate component (A) with a polyol component (B) containing 70 to 100% by mass of a polyether polyurethane polyol having a number average molecular weight of 200 to 3000,
4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and xylene contained in 100% by mass of the total of the polyisocyanate component (A) and the polyol component (B) A step of preparing an adhesive composition in which the total amount of at least one isocyanate component selected from the group consisting of diisocyanates is 10 to 34% by mass.
(III) A step of applying the 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 laminating 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 comprising a transparent substrate 1, a white ink layer, an adhesive layer, and a substrate 2 having an oxygen permeability of 100 cc (m ² , 24 hr, 1 atm, 25 ° C.) or less in this order, A method for producing a laminate comprising the following steps (I) to (III) and (VII) to (IX).
(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% by mass of amino in 100% by mass of solid content of the ink composition. A step of preparing a white ink composition containing a silane coupling agent.
(II-1) After reacting 4,4′-diphenylmethane diisocyanate with a polyol essentially comprising a polyether polyol under conditions of an excess of isocyanate groups,
At least one bifunctional isomer selected from the group consisting of a trimer of a bifunctional isocyanate monomer, a burette in which water is added to a bifunctional isocyanate monomer, and an adduct in which a monoalcohol is added to a bifunctional isocyanate monomer. A modified isocyanate monomer,
If necessary, at least one isocyanate component selected from the group consisting of 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and xylene diisocyanate,
A urethane prepolymer (a) having an isocyanate group;
4,4′-diphenylmethane diisocyanate;
At least one bifunctional isomer selected from the group consisting of a trimer of a bifunctional isocyanate monomer, a burette in which water is added to a bifunctional isocyanate monomer, and an adduct in which a monoalcohol is added to a bifunctional isocyanate monomer. And a modified isocyanate monomer.
Preparing a polyisocyanate component (A), which can further include at least one isocyanate component selected from the group consisting of 2,4′-diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and xylene diisocyanate;
(II-2) mixing the polyisocyanate component (A) with a polyol component (B) containing 70 to 100% by mass of a polyether polyurethane polyol having a number average molecular weight of 200 to 3000,
4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and xylene contained in a total of 100% by mass of the polyisocyanate component (A) and the polyol component (B) A step of preparing an adhesive composition in which the total amount of at least one isocyanate component selected from the group consisting of diisocyanates is 10 to 34% by mass .
(III) A step of applying the 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 substrate 2 to form a precursor of an adhesive layer.
(VIII) a step of overlaying the white ink layer on a precursor of the adhesive layer.
(IX) A step of curing the precursor of the adhesive layer to form an adhesive layer.