WO2021039559A1

WO2021039559A1 - Gas barrier laminate, and packaging material

Info

Publication number: WO2021039559A1
Application number: PCT/JP2020/031385
Authority: WO
Inventors: 友昭原田
Original assignee: Dic株式会社
Priority date: 2019-08-27
Filing date: 2020-08-20
Publication date: 2021-03-04
Also published as: JPWO2021039559A1; CN114206612A; JP7228107B2

Abstract

The purpose of the present invention is to provide: a laminate having better gas barrier properties than a conventional gas barrier laminate; and a packaging material using said laminate.　To achieve the purpose, the present invention provides a laminate comprising: a base material made of biaxially stretched polypropylene; an aluminum oxide layer disposed on the base material; a gas barrier coating agent layer disposed on the aluminum oxide layer; and a gas barrier adhesive layer disposed on the gas barrier coating agent layer.

Description

Gas barrier laminate, packaging material

The present invention relates to a gas barrier laminate and a packaging material obtained by using the gas barrier laminate.

Packaging materials used for packaging foods, pharmaceuticals, etc. are required to prevent deterioration of their contents, especially oxidation by oxygen. In response to this demand, conventionally, a barrier film made of a resin having a relatively high oxygen barrier property and a laminate (laminated film) using the barrier film as a film base material have been used.
Conventionally, as the oxygen barrier resin, a resin containing a highly hydrophilic hydrogen-bonding group in the molecule represented by polyacrylic acid or polyvinyl alcohol has been used. In recent years, research has been conducted to further improve the barrier properties of these oxygen barrier resins.

Japanese Unexamined Patent Publication No. 2019-130737 Japanese Unexamined Patent Publication No. 2019-34460

However, with the conventional gas barrier laminate, sufficient gas barrier properties cannot always be obtained, a good coating appearance cannot be achieved, and the demand for the gas barrier laminate cannot be satisfied.

The present invention has been made in view of such circumstances, and an object of the present invention is to provide a laminate having better gas barrier properties than a conventional gas barrier laminate, and a packaging material using the laminate.

The present invention comprises a base material made of biaxially stretched polypropylene, an aluminum oxide layer arranged on the base material, a gas barrier coating agent layer arranged on the aluminum oxide layer, and a gas barrier coating agent layer. With respect to a laminate having a gas barrier adhesive layer arranged in.

In the present invention, the gas barrier coating agent is a coating agent containing a resin (A) having a carboxyl group, a divalent metal compound (B), and an alcohol (C), and the alcohol (C) in the composition. It is preferable that the content is 85 to 98 wt% and the water content in the composition is 1% or less.

In the present invention, the resin (A) having a carboxyl group is at least one selected from homopolymers or copolymers of monomers selected from acrylic acid, methacrylic acid, maleic acid, itaconic acid and aspartic acid. It is preferable to have.

In the present invention, it is preferable that the divalent metal compound (B) is at least one selected from a zinc compound, a magnesium compound and a calcium compound.

In the present invention, it is preferable that the alcohol (C) is at least one selected from methanol, ethanol, propanol and butanol.

The present invention also relates to a packaging material made of the laminate.

According to the laminate of the present invention, it is possible to provide a packaging material having excellent gas barrier properties.

<Laminated body>
The laminate of the present invention comprises a base material made of biaxially stretched polypropylene, an aluminum oxide layer arranged on the base material, a gas barrier coating agent layer arranged on the aluminum oxide layer, and the gas barrier coating agent. It has a gas barrier adhesive layer arranged on the layer. In addition to these layers, a sealant layer, a printing layer, an anchor coat layer and the like may be provided. Hereinafter, the configuration of the present invention will be described in detail.

(Base material)
The base material used for the laminate of the present invention is made of biaxially stretched polypropylene. Examples of the raw material include a propylene homopolymer, a propylene resin composed of a copolymer of propylene and another monomer, and a mixture of a propylene homopolymer and a copolymer. A film or sheet made of these raw materials (unless otherwise specified below, the film is also a general term for a film and a sheet) is formed by a single layer or a coextrusion method of two or more layers and stretched in the biaxial direction. Can be used.

As a method of stretching in two directions, a conventionally known method can be used. For example, the raw material is melted by an extruder, extruded by an annular die or a T die, and rapidly cooled to be oriented substantially indefinitely. Produce no unstretched film. After that, this unstretched film is stretched by a method such as tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, and tubular simultaneous biaxial stretching, and is perpendicular to the film flow direction and the film flow direction. It can be manufactured by stretching in the (horizontal axis) direction. The draw ratio can be appropriately selected depending on the polypropylene raw material, but is usually preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction, respectively.

The film thickness of the base material is not particularly limited, and may be appropriately selected in the range of 1 to 300 μm from the viewpoint of moldability and transparency. Since suitable strength, rigidity, and ease of processing can be obtained, the film thickness of the base material is preferably 1 to 100 μm, more preferably 20 to 50 μm.

The substrate used in the present invention preferably has a plane orientation coefficient Δ according to the phase difference measurement method in the range of 0.005 to 0.020. This makes it possible to improve the adhesion between the aluminum oxide layer and the base material, which will be described later, to a level that can sufficiently withstand boiling and retort treatment.

As a method of adjusting the surface orientation coefficient Δ of the base material in the range of 0.005 to 0.020, for example, a heat fixing step is performed after biaxial stretching, and conditions for biaxial stretching and heat fixing are appropriately selected. A method of controlling the plane orientation coefficient Δ can be mentioned. For example, the plane orientation coefficient Δ can be adjusted within a desired range by performing heat fixation at a low temperature for a long time after biaxial stretching. It is also possible to modify the surface so that the surface orientation coefficient Δ is in the range of 0.005 to 0.020 by surface treatment such as reactive ion etching (RIE) treatment described later. A commercially available product in which the surface orientation coefficient Δ is adjusted in the range of 0.005 to 0.020 in advance may be used, or the surface of the base material may be modified immediately before the aluminum oxide layer is formed.

Further, the base material used in the present invention preferably has an orientation angle measured by the phase difference measurement method of 50 ° to 90 ° or −50 ° to −90 ° with respect to the flow direction. This makes it possible to improve the adhesion between the aluminum oxide layer and the base material, which will be described later, to a level that can sufficiently withstand boiling and retort treatment. Here, the orientation angle is defined as + if the molecular chains are tilted to the left and aligned to the right, and-if the molecular chains are tilted to the right, with the flow direction as 0 °.

The orientation angle in the flow direction can be obtained by using a method such as a phase difference measurement method using visible light or a molecular orientation measurement method using a microwave, but in the case of a molecular orientation measurement method using a microwave. The variation of the measured value by the measurer becomes large. On the other hand, the phase difference measuring method can perform stable measurement regardless of the measurer, has little variation in the measurer, and can accurately measure the orientation angle. Therefore, it is preferable to adopt the phase difference measurement method for measuring the orientation angle with respect to the flow direction.

Such a substrate is obtained through biaxial stretching and thermal fixation. The orientation angle can be controlled by appropriately selecting the conditions of biaxial stretching and thermal fixation. For example, by cutting out the central portion with respect to the flow direction after biaxial stretching and using it, the orientation angle of the base material can be selected within a desired range.

The base material may contain additives as needed. Specifically, improve workability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, mold releasability, flame retardancy, antifungal properties, electrical properties, strength, etc. For the purpose of modification, plastic compounding agents and additives such as lubricants, cross-linking agents, antioxidants, ultraviolet absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents and pigments can be added. The amount of additive added should be adjusted within a range that does not affect other performance.

(surface treatment)
In order to improve the adhesion of the aluminum oxide layer, the substrate is physically treated with some surface treatment, such as corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, etc. Treatment, chemical treatment such as oxidation treatment using chemicals, and other treatments may be performed. In particular, the discharge treatment is preferable because the surface orientation coefficient Δ of the base material can be adjusted within a desired range. The discharge treatment is not particularly limited, but the RIE treatment is preferable.

The RIE processing can be performed using, for example, a take-up type in-line device, and a planar type processing device that applies a voltage to the cooling drum on which the base material is installed can be used. In the method of RIE-treating a base material with a planar type treatment device, an electrode (cathode) is placed inside a treatment roll (cooling roll), and ions in plasma are transferred to the surface of the base material while being conveyed along the treatment roll. Let it act and perform RIE treatment. According to such a method, the base material can be placed at a position close to the cathode, and the RIE treatment can be performed by obtaining a high self-bias.

Alternatively, the RIE treatment can be performed using a hollow anode plasma processing device. The holoanode plasma processing apparatus includes, for example, a processing roll that functions as an anode. The cathode and the shielding plates arranged at both ends of the cathode are arranged outside the processing roll so as to face the processing roll, and the cathode is formed in a box shape having an opening. The opening of the cathode is opened so as to face the processing roll, and the shielding plate has a curved surface shape along the processing roll. A gas introduction nozzle is arranged above the cathode to introduce gas into the gap between the processing roll and the cathode and between the processing roll 7 shielding plate. The matching box is located behind the cathode.

In order to perform RIE treatment of a base material with such a holoanode plasma processing device, a voltage is applied from the matching box to the cathode while transporting the base material along the treatment roll, and the treatment roll and cathode into which gas is introduced and the cathode and The plasma is generated between the shielding plates, and the radicals in the plasma are attracted toward the processing roll which is the anode, so that the radicals act on the surface of the base material.

In the RIE treatment, it is preferable to incorporate a magnet in the holo anode electrode and use a magnetically assisted holo anode. This makes it possible to perform more powerful and stable plasma surface treatment at high speed. The magnetic field generated from the magnetic electrode further enhances the plasma confinement effect, and a high ionic current density can be obtained with a large self-bias.

For example, argon, oxygen, nitrogen, and hydrogen can be used as the gas type for pretreatment by RIE. These gases may be used alone or in combination of two or more. In the RIE processing, the processing can be continuously performed by using two or more processing devices. At this time, the two or more processing devices used do not have to be the same. For example, it is also possible to process the base material with a planar type processing apparatus and then continuously perform the processing with a holoanodic plasma processing apparatus.

(Anchor coat layer)
In the laminate of the present invention, an anchor coat layer may be provided on the base material prior to the formation of the aluminum oxide layer. The anchor coat layer can be formed by applying an anchor coat agent on a substrate and drying it. As a result, the adhesion between the base material and the aluminum oxide layer can be improved, and the flatness of the formed surface of the aluminum oxide layer can be improved by the leveling action of the anchor coating agent, and uniform aluminum oxide with few film defects such as cracks can be improved. A thin film can be formed.

Examples of the anchor coating agent include solvent-soluble or water-soluble polyester resin, isocyanate resin, urethane resin, acrylic resin, vinyl alcohol resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, oxazoline group-containing resin, and modified styrene. Examples thereof include resins, modified silicone resins and alkyl titanates. These can be used alone or in combination of two or more.

The film thickness of the anchor coat layer is not particularly limited, but is preferably about 5 nm to 5 μm, and more preferably 10 nm to 1 μm. As a result, a uniform layer in which internal stress is suppressed can be formed on the base material.

When the anchor coat layer is provided, it is also preferable to perform a discharge treatment on the surface of the base material prior to forming the anchor coat layer in order to improve the coatability and adhesiveness of the anchor coat agent.

(Aluminum oxide layer)
The aluminum oxide layer is a layer whose main component is aluminum oxide. Here, the main component means that more than 50% by mass of the components constituting the aluminum oxide layer is aluminum oxide. It is preferable that 70% by mass or more of the components constituting the aluminum oxide layer is aluminum oxide, more preferably 90% by mass or more, and ideally 100% by mass. Aluminum oxide, AlO, consists _Al 2 O, at least one or more kinds of various aluminum oxides such as Al ₂ O _3, the content of various aluminum oxide can be adjusted by making the conditions of thin layer.

The aluminum oxide layer preferably has an oxygen to aluminum ratio (O / Al ratio) calculated by the XPS measurement method of 1.0 to 1.5. As a result, it is transparent and exhibits high adhesion to the substrate. When the O / Al ratio is in the above range, sufficient barrier properties can be ensured, good transparency can be obtained, and film defects such as cracks are less likely to occur.

The aluminum oxide layer may have an oxygen atom concentration gradient in the layer in the stacking direction. For example, the O / Al ratio may increase from the surface of the aluminum oxide layer on the substrate side to the surface opposite to the substrate. Only one layer of the aluminum oxide layer may be provided, or two or more layers formed by the same or different methods may be provided.

The film thickness of the aluminum oxide layer is preferably 5 nm to 300 nm, and more preferably 10 nm to 300 nm. When the film thickness of aluminum oxide is within the above range, a uniform layer can be formed, and sufficient barrier properties can be ensured.

The surface roughness of the aluminum oxide layer is preferably 3.5 μm or less, more preferably 2.5 μm or less, and even more preferably 2.0 μm or less. The lower limit of the surface roughness Rm is not particularly limited, but is 1.0 μm or more as an example. Here, the surface roughness of the aluminum oxide layer means the surface roughness on the surface of the aluminum oxide layer opposite to the base material, and the AFM unevenness image measured by an atomic force microscope (hereinafter referred to as “AFM”) is roughened. It is a value of roughness Rms (square mean square root roughness) obtained by Sas analysis.

The surface roughness of the aluminum oxide layer is affected by the surface roughness of the base material, the presence or absence of the anchor coat layer, the particle size of the particles forming the aluminum oxide layer, the film thickness of the aluminum oxide layer, etc. When the surface roughness of the received aluminum oxide layer is within the above range, the gas barrier property of the laminated body can be improved.

Further, the average particle size of the particles forming the aluminum oxide layer is preferably 20 nm or less. As a result, the aluminum oxide layer can be filled with a high density, and the unevenness of the surface of the base material can be efficiently covered without gaps, so that a laminated body having excellent gas barrier properties can be obtained. The average particle size of the particles forming the aluminum oxide layer is more preferably 15 nm or less, and further preferably 10 nm or less. The lower limit is not particularly limited. The average particle size of the particles forming the aluminum oxide layer can be obtained by analyzing the AFM uneven image as well as the measurement of the surface roughness of the aluminum oxide layer.

The aluminum oxide layer can be formed by a vacuum deposition method, a sputtering method, an ion plating method, a chemical vapor deposition method (CVD), or the like. The vacuum deposition method is preferable when productivity is taken into consideration. When the aluminum oxide layer is formed by the vacuum vapor deposition method, a means for generating high-density plasma may be used in combination. As a heating method for the vapor-deposited raw material, an electron beam (EB) method, a high-frequency induction heating method, a resistance heating method, or the like is used. By applying high-density plasma having high energy to the vaporized particles vaporized or sublimated by the vacuum vapor deposition method, the film quality of the aluminum oxide layer such as density can be improved and the barrier property can be improved. Examples of means for generating high-density plasma include inductively coupled (ICP) plasma, helicon wave plasma, microwave plasma, and hollow cathode discharge.

(Gas barrier coating agent layer)
In the laminate of the present invention, a gas barrier coating agent layer is formed on the aluminum oxide layer to improve the gas barrier property of the laminate, protect the aluminum oxide layer, and form a gas barrier adhesive layer or an arbitrarily formed printing layer. Improves adhesion.

The gas barrier coating agent of the present invention is a coating agent containing a resin (A) having a carboxyl group, a divalent metal compound (B), and an alcohol (C), and the alcohol (C) in the composition. The content is 85 to 98 wt%, and the water content in the composition is 1% or less.

<Resin (A) having a carboxyl group>
The resin (A) having a carboxyl group of the present invention may contain carboxylic acid anhydride as a carboxyl group. The resin (A) having a carboxyl group is preferably at least one selected from homopolymers or copolymers of monomers selected from acrylic acid, methacrylic acid, maleic acid, itaconic acid and aspartic acid. ..

Further, the resin (A) having a carboxylic acid group preferably has an acid value of 50 to 800 mgKOH / g because the barrier performance is improved. Particularly preferably, it is 80 to 800 mgKOH / g. If the acid value is 80 mgKOH / g or more, ionic bonding is sufficiently advanced and high barrier performance can be obtained.

(Acid value measurement method)
The acid value is the number of mg of potassium hydroxide required to neutralize the acid content present in 1 g of the sample. Specifically, the weighed sample is dissolved in an appropriate solvent in which the sample dissolves, for example, a solvent of toluene / methanol = 70/30 in volume ratio, and a few drops of a 1% phenolphthalein alcohol solution are added dropwise thereto. It can be measured by a method of dropping a 0.1 mol / L potassium hydroxide alcohol solution and confirming the discoloration point, and can be calculated by the following formula.

Acid value measurement method-1
Acid value (mgKOH / g) = (V × F × 5.61) / S
V: Amount of 0.1 mol / L potassium hydroxide alcohol solution used (mL)
F: Titer of 0.1 mol / L potassium hydroxide alcohol solution S: Sample collection amount (g)
5.61: Potassium hydroxide equivalent amount (mg) in 1 mL of 0.1 mol / L potassium hydroxide alcohol solution

When the sample is a resin solution, the resin acid value (mgKOH / g) can be calculated by the following formula.

Resin acid value (mgKOH / g) = Acid value of resin solution (mgKOH / g) / NV (%) x 100 NV: Non-volatile content (%)

In addition, if the solubility of the sample in an organic solvent is low and it is difficult to measure due to precipitation, etc., the acid value can also be measured by the following method.

Acid value measurement method-2
The acid value (mgKOH / g-resin) is a coefficient (f) obtained from a calibration line prepared with a chloroform solution of maleic anhydride using FT-IR (FT-IR4200 manufactured by Nippon Kogaku Co., Ltd.), maleic anhydride. Calculated by the following formula using the absorbance (I) of the expansion and contraction peak (1780 cm-1) of the anhydrous ring of maleic anhydride and the absorbance (II) of the expansion and contraction peak (1720 cm-1) of the carbonyl group of maleic acid in an acid-modified polyolefin solution. Is the value.
Acid value (mgKOH / g-regin) = [(Absorptiometry (I) × (f) × 2 × Molecular weight of potassium hydroxide × 1000 (mg) + Absorbance (II) × (f) × Molecular weight of potassium hydroxide × 1000 (Mg)) / Molecular weight of maleic anhydride]
Maleic anhydride molecular weight: 98.06, potassium hydroxide molecular weight: 56.11

The resin (A) having a carboxyl group of the present invention is not particularly limited in molecular weight, but is preferable from the viewpoint of coating film moldability having a number average molecular weight of 300 to 2,000,000. Particularly preferably, it is 500 to 1,000,000.
The weight average molecular weight of the resin (A) having a carboxyl group of the present invention can be calculated by measuring by the method of gel permeation chromatography (GPC).

The resin (A) having a carboxyl group of the present invention is not particularly limited as long as it is a resin having a carboxyl group in its structure, but is preferably a carboxyl group-containing vinyl resin.

(Carboxyl group-containing vinyl resin)
Examples of the carboxyl group-containing vinyl resin include polymers of polymerizable unsaturated monomers having a carboxyl group. Examples of the polymerizable unsaturated monomer having a carboxyl group include unsaturated carboxylic acids such as (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, crotonic acid, itaconic acid, maleic acid and fumaric acid;

Various unsaturated dicarboxylic acids such as monomethyl itaconic acid, mono-n-butyl itaconic acid, monomethyl maleate, mono-n-butyl maleate, monomethyl fumarate, mono-n-butyl fumarate, and saturated monohydric alcohols. Monoesters (half esters);

Monovinyl esters of various saturated dicarboxylic acids such as monovinyl adipic acid or monovinyl succinate;

Addition reaction products of various saturated polycarboxylic acid anhydrides such as succinic anhydride, glutaric anhydride, phthalic anhydride or trimellitic anhydride and various hydroxyl group-containing vinyl monomers; Examples thereof include various monomers obtained by addition-reacting various carboxyl group-containing monomers as described above with lactones.

The resin (A) having a carboxyl group of the present invention may be a homopolymer of the above-mentioned polymerizable unsaturated monomer having a carboxyl group, or the polymerizable unsaturated monomer having a carboxyl group. It may be a copolymer using a plurality. Further, it may be a copolymer of a polymerizable unsaturated monomer having a carboxyl group and another monomer copolymerizable.

Examples of the monomer copolymerizable with the polymerizable unsaturated monomer having a carboxyl group include the following.

(1) Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, -n-butyl (meth) acrylate, -t-butyl (meth) acrylate, hexyl (meth) acrylate , (Meta) hepcil acrylate, (meth) octyl acrylate, (meth) nonyl acrylate, (meth) decyl acrylate, (meth) dodecyl acrylate, (meth) tetradecyl acrylate, (meth) hexadecyl acrylate, (Meta) acrylic acid esters having an alkyl group having 1 to 22 carbon atoms such as stearyl (meth) acrylate, octadecyl (meth) acrylate, and docosyl (meth) acrylate;

(2) (Meta) acrylic having a fat-type alkyl group such as cyclohexyl (meth) acrylate, isoboronyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, etc. Acrylic acids;

(3) Benoxyethyl benzoyl (meth) acrylate, benzyl (meth) acrylate, phenylethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, 2- (meth) acrylate (Meta) acrylic acid esters having an aromatic ring such as hydroxy-3-phenoxypropyl;

(4) Hydrochiethyl (meth) acrylate; hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, glycerol (meth) acrylate; lactone-modified hydroxyethyl (meth) acrylate, polyethylene (meth) acrylate Acrylic acid esters having a hydroxyalkyl group such as (meth) acrylic acid ester having a polyalkylene glycol group such as glycol and (meth) acrylic acid polypropylene glycol;

(5) Unsaturated dicarboxylic acid esters such as dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dimethyl itaconic acid, dibutyl itaconic acid, methyl ethyl fumarate, methyl butyl fumarate, and methyl ethyl itaconic acid;

(6) Styrene derivatives such as styrene, α-methylstyrene and chlorostyrene;

(7) Diene compounds such as butadiene, isoprene, piperylene, and dimethyl butadiene;

(8) Vinyl halides such as vinyl chloride and vinyl bromide and vinylidene halides;

(9) Unsaturated ketones such as methyl vinyl ketone and butyl vinyl ketone;

(10) Vinyl esters such as vinyl acetate and vinyl butyrate;

(11) Vinyl ethers such as methyl vinyl ether and butyl vinyl ether;

(12) Vinyl cyanides such as acrylonitrile, methacrylonitrile, and vinylidene cyanide;

(13) Acrylamide and its alkyd-substituted amides;

(14) N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;

(15) Fluorine-containing α-olefins such as vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, pentafluoropropylene or hexafluoropropylene; or trifluoromethyltrifluorovinyl ether, penta. Fluoroalkyl perfluorovinyl ethers having 1 to 18 carbon atoms in a (per) fluoroalkyl group, such as fluoroethyl trifluorovinyl ether or heptafluoropropyl trifluorovinyl ether; 2,2,2-trifluoroethyl (meth) ) Acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 2H, 2H-heptadecafluorodecyl (meth) acrylate or Fluorine-containing ethylenically unsaturated monomers such as (per) fluoroalkyl (meth) acrylates having 1 to 18 carbon atoms in a (per) fluoroalkyl group such as perfluoroethyloxyethyl (meth) acrylate;

(16) Cyril group-containing (meth) acrylates such as γ-methacryloxypropyltrimethoxysilane;

(17) N, N-dialkylaminoalkyl (meth) acrylate such as N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate or N, N-diethylaminopropyl (meth) acrylate, etc. Can be mentioned.

These polymerizable unsaturated monomers may be used alone or in combination of two or more.

The resin (A) having a carboxyl group can be obtained by polymerizing (copolymerizing) using a known and commonly used method, and the copolymerization form thereof is not particularly limited. It can be produced by addition polymerization in the presence of a catalyst (polymerization initiator), and may be any of a random copolymer, a block copolymer, a graft copolymer and the like. Further, as the copolymerization method, known polymerization methods such as a massive polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method can be used.

<Divalent metal compound (B)>
The metal compound (B) of the present invention is characterized by being a divalent metal compound.
The divalent metal compound (B) is a compound of a divalent metal. Examples of the divalent metal compound (B) include zinc compounds, magnesium compounds, calcium compounds, manganese compounds, iron compounds, cobalt compounds, nickel compounds, copper compounds and the like, and zinc compounds, magnesium compounds and calcium compounds are particularly preferable. is there. These metal compounds may be used alone or in combination of two or more.

The divalent metal compound (B) is preferably a divalent metal oxide, a hydroxide, or a carbonate, and may be a mixture thereof.
Specific compounds of the divalent metal compound (B) are preferably zinc oxide, magnesium oxide and calcium oxide, and particularly preferably zinc oxide and magnesium oxide.

The divalent metal compound (B) is preferably in the form of particles. More preferably, the fine particles have an average particle diameter of 500 nm or less and 10 nm or more. Particularly preferably, it is fine particles of 20 nm to 300 nm.
The average particle size here can be measured using a dynamic light scattering type particle size distribution measuring device, for example, LB-500 (manufactured by HORIBA, Ltd.).

<Alcohol (C)>
As the alcohol (C) of the present invention, a known and commonly used alcohol can be used. Specific examples thereof include methanol, ethanol, propanol, butanol, hexanol, pentanol and the like. Methanol, ethanol, propanol and butanol are preferable, and propanol is particularly preferable.

<Gas barrier coating agent>
The gas barrier coating agent of the present invention is characterized by containing the above-mentioned resin (A) having a carboxyl group, a divalent metal compound (B), and an alcohol (C). Among them, the content of alcohol (C) is 85 to 98 wt%, and the water content in the composition is 1% or less. When the alcohol (C) and water are in this range, the divalent metal compound (B) is stably present in the composition and forms an ionic bond with the resin (A) having a carboxyl group for the first time when the coating is dried. Demonstrates gas barrier properties. Since the composition can be stably stored in a normal state, it can be very suitably used as a coating agent for a gas barrier, and a one-component coat layer having a gas barrier property can be formed.

In the gas barrier coating agent of the present invention, the non-volatile content is 1 wt% to 15 wt% in the composition. The total amount of the resin (A) having a carboxyl group and the divalent metal compound (B) in the total amount of the non-volatile content is preferably 90 to 100 wt%. Within this range, the gas barrier property can be sufficiently exhibited. Particularly preferably, it is 95 to 100 wt%. The ratio of the resin (A) having a carboxyl group and the divalent metal compound (B) is the divalent metal compound with respect to the total amount of the resin (A) having a carboxyl group and the divalent metal compound (B). (B) is preferably 15 to 60 wt%. Within this range, gas barrier properties and coatability can be well compatible. Particularly preferably, it is 20 to 50 wt%.

The gas barrier coating agent of the present invention may contain a material other than the resin (A) having a carboxyl group, the divalent metal compound (B), and the alcohol (C) described above.

(solvent)
The gas barrier coating agent of the present invention may contain a solvent other than alcohol (C), and is preferably a solvent compatible with alcohol (C), and examples thereof include ethylene glycol, propylene glycol, and glycerin.

(Additive)
The composition of the present invention may contain various additives as long as the effects of the present invention are not impaired. Additives include, for example, coupling agents, silane compounds, phosphoric acid compounds, organic fillers, inorganic fillers, stabilizers (antioxidants, heat stabilizers, UV absorbers, etc.), plasticizers, antistatic agents, lubricants, etc. Examples thereof include antiblocking agents, colorants, crystal nucleating agents, oxygen trapping agents (compounds having an oxygen trapping function), tackifiers and the like. These various additives are used alone or in combination of two or more.

Examples of the coupling agent include known and commonly used ones, and examples thereof include a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, and an aluminum coupling agent.

As the silane coupling agent, known and commonly used agents may be used, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-( 3,4 Epoxycyclohexyl) Epyl group-containing silane coupling agent such as ethyltrimethoxysilane; 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl Amino group-containing silane coupling agent such as -N- (1,3-dimethylbutylidene) propylamine, N-phenyl-γ-aminopropyltrimethoxysilane; 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyl Examples thereof include (meth) acryloyl group-containing silane coupling agents such as triethoxysilane; isocyanate group-containing silane coupling agents such as 3-isocyanatepropyltriethoxysilane.

Examples of the titanium coupling agent include isopropyltriisostearoyl titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropylisostearoyl diacrylic titanate, isopropyltris (dioctylpyrophosphate) titanate, and tetraoctylbis (ditridecyl). Examples thereof include phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, and bis (dioctylpyrophosphate) ethylene titanate.

Examples of the zirconium coupling agent include zirconium acetate, ammonium zirconium carbonate, zirconium fluoride and the like.

Examples of the aluminum cup rig include acetalkoxyaluminum diisopropyrate, aluminum diisopropoxymonoethylacetate, aluminumtrisethylacetate, and aluminumtrisacetylacetonate.

Examples of the silane compound include alkoxysilane, silazane, and siloxane. Examples of alkoxysilanes include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, and hexyltri. Examples thereof include methoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis (trimethoxysilyl) hexane, trifluoropropyltrimethoxysilane and the like. Examples of the silazane include hexamethyldisilazane and the like. Examples of the siloxane include hydrolyzable group-containing siloxane.

Among the additives, examples of the inorganic filler include inorganic substances such as metals, metal oxides, resins, and minerals, and composites thereof. Specific examples of the inorganic filler include silica, alumina, titanium, zirconia, copper, iron, silver, mica, talc, aluminum flakes, glass flakes, clay minerals and the like.

Examples of the compound having an oxygen trapping function include low molecular weight organic compounds that react with oxygen such as hindered phenol compounds, vitamin C, vitamin E, organic phosphorus compounds, gallic acid, and pyrogallol, and cobalt, manganese, nickel, and iron. , Transition metal compounds such as copper and the like.

Examples of the tackifier include xylene resin, terpene resin, phenol resin, rosin resin and the like. By adding a tackifier, the adhesiveness to various substrates immediately after application can be improved. The amount of the tackifier added is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the total amount of the resin composition.

(Gas barrier adhesive layer)
The gas barrier adhesive layer is a cured coating film of the gas barrier adhesive and is arranged on the gas aria coating layer. The gas barrier adhesive that can be used is not particularly limited as long as it has gas barrier properties. In the present specification, the gas barrier adhesive means that ^{the cured coating film of the adhesive applied at 5 g / m 2} (solid content) has an oxygen barrier property of 300 cc / m ² / day / atm or less, or a steam barrier property. It means one that satisfies at least one of the conditions of 120 g / m ^{2 / day or less.} Examples of commercially available products include the "PASLIM" series such as PASLIM VM001 and PASLIM J350X manufactured by DIC Corporation, and the "Maxive" manufactured by Mitsubishi Gas Chemical Company.

The adhesive having gas barrier properties used in the present invention includes a polyol composition (A) containing at least one of the following polyester polyols (A1) to (A5), and at least two isocyanate groups in one molecule. A two-component adhesive composed of a polyisocyanate composition (B) containing a compound (hereinafter, also simply referred to as an isocyanate compound) is preferably used.

(1) A polyester polyol (A1) obtained by reacting a polyester polyol having three or more hydroxyl groups with a carboxylic acid anhydride or a polycarboxylic acid.
(2) Polyester polyol (A2) having a polymerizable carbon-carbon double bond
(3) Polyester polyol having a glycerol skeleton (A3)
(4) Polyester polyol (A4) obtained by polycondensing an ortho-oriented polyvalent carboxylic acid and a polyhydric alcohol.
(5) Polyester polyol having an isocyanul ring (A5)

The polyester polyol (A1) is obtained by reacting a polyester polyol (a1) having three or more hydroxyl groups with a carboxylic acid anhydride or a polyvalent carboxylic acid, and has at least one carboxyl group and two or more hydroxyl groups. Have. The polyester polyol (a1) can be obtained by making a part of the polyvalent carboxylic acid or polyhydric alcohol trivalent or higher.

The polyvalent carboxylic acid used for preparing the polyester polyol (A1) preferably contains at least one of orthophthalic acid and orthophthalic anhydride. The polyester polyol obtained by using these compounds as a polyvalent carboxylic acid has excellent gas barrier properties and adhesiveness. It is presumed that the reason why the gas barrier property of the adhesive is excellent by using orthophthalic acid and orthophthalic anhydride is that the rotation of the polyester chain obtained by using orthophthalic acid and its acid anhydride is suppressed. It is presumed that the reason why the adhesiveness is excellent is that the polyester chain exhibits non-crystallinity due to the asymmetry, and sufficient substrate adhesion is imparted.

Examples of the trivalent or higher polyvalent carboxylic acid include trimellitic acid and its acid anhydride, pyromellitic acid and its acid anhydride. In order to prevent gelation during synthesis, it is preferable to use a trivalent carboxylic acid as a trivalent or higher polyvalent carboxylic acid.

Other polyvalent carboxylic acids may be copolymerized as long as the effects of the present invention are not impaired. Specifically, aliphatic polyvalent carboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, and dodecanediocarboxylic acid; unsaturated bond-containing polyvalent carboxylic acids such as maleic anhydride, maleic acid, and fumaric acid; , 3-Cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and other alicyclic polyvalent carboxylic acids; terephthalic acid, isophthalic acid, pyromellitic acid, trimellitic acid, 1,4-naphthalenedicarboxylic acid, 2,5 -Naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid and acid anhydrides or ester-forming derivatives of these dicarboxylic acids , P-Hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid and aromatic polyvalent carboxylic acids such as ester-forming derivatives of these dihydroxycarboxylic acids, and one or more are used in combination. be able to. Of these, succinic acid, 1,3-cyclopentanedicarboxylic acid, isophthalic acid and acid anhydrides thereof are preferable.

The polyhydric alcohol used for preparing the polyester polyol (A1) preferably contains at least one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol. It is presumed that the smaller the number of carbon atoms between oxygen atoms, the less flexible the molecular chain is and the more difficult it is for oxygen to permeate. Therefore, it is particularly preferable to use ethylene glycol.

Examples of the trihydric or higher polyhydric alcohol include glycerin, trimethylolpropane, trimethylolethane, tris (2-hydroxyethyl) isocyanurate, 1,2,4-butanetriol, pentaerythritol, dipentaerythritol and the like. Be done. In order to prevent gelation during synthesis, it is preferable to use a trihydric alcohol as a trihydric or higher polyhydric alcohol.

Other polyvalent carboxylic acids may be copolymerized as long as the effects of the present invention are not impaired. Specifically, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetra. Aliphatic diols such as ethylene glycol, dipropylene glycol and tripropylene glycol; hydroquinone, resorcinol, catechol, naphthalenediol, biphenol, bisphenol A, hisphenol F, tetramethylbiphenol, these ethylene oxide extensions, hydrogenated fats Aromatic polyvalent phenols such as ring family can be exemplified.

The polyester polyol (A1) reacts the polyvalent carboxylic acid or its acid anhydride with the polyester polyol (a1) having three or more hydroxyl groups, which is a reaction product of the above-mentioned polyvalent carboxylic acid and polyhydric alcohol. You can get it. The ratio of the hydroxyl group to be reacted with the polyvalent carboxylic acid is preferably 1/3 or less of the hydroxyl group contained in the polyester polyol (a1). The polyvalent carboxylic acid or its acid anhydride to be reacted with the polyester polyol (a1) is preferably divalent or trivalent. Succinic anhydride, maleic anhydride, 1,2-cyclohexanedicarboxylic acid anhydride, 4-cyclohexene-1,2-dicarboxylic acid anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, phthalic anhydride, 2, Examples thereof include, but are not limited to, 3-naphthalenedicarboxylic acid anhydride and trimellitic acid anhydride.

The polyester polyol (A2) having a polymerizable carbon-carbon double bond can be obtained by using a component having a polymerizable carbon-carbon double bond as a polyvalent carboxylic acid and a polyhydric alcohol.

Maleic anhydride, maleic acid, fumaric acid, 4-cyclohexene-1,2-dicarboxylic acid and its acid anhydride, 3-methyl-4-cyclohexene-1, as polyvalent carboxylic acids having a polymerizable carbon-carbon double bond. , 2-Dicarboxylic acid and its acid anhydride and the like. Among them, maleic anhydride, maleic acid, and fumaric acid are preferable because it is presumed that the smaller the number of carbon atoms is, the less flexible the molecular chain is and the less oxygen is permeated.

Other polyvalent carboxylic acids may be copolymerized as long as the effects of the present invention are not impaired. Specifically, aliphatic polyvalent carboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid; alicyclic groups such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid. Polyvalent carboxylic acid; orthophthalic acid, terephthalic acid, isophthalic acid, pyromellitic acid, trimellitic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyl Dicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid and acid anhydride or ester-forming derivative of these dicarboxylic acids, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid And aromatic polyvalent carboxylic acids such as ester-forming derivatives of these dihydroxycarboxylic acids can be mentioned, and one or more of them can be used in combination. Moreover, these acid anhydrides can also be used. Of these, succinic acid, 1,3-cyclopentanedicarboxylic acid, orthophthalic acid, acid anhydrides of orthophthalic acid, and isophthalic acid are preferable, and orthophthalic acid and its acid anhydride are more preferable, in order to obtain gas barrier properties.

Examples of the polyhydric alcohol having a polymerizable carbon-carbon double bond include 2-butene-1,4-diol and the like.

Other polyhydric alcohols may be copolymerized as long as the effects of the present invention are not impaired. Specifically, ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, cyclohexanedimethanol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol. , Dimethylbutanediol, Butylethylpropanediol, Diethylene glycol, Triethylene glycol, Tetraethylene glycol, Dipropylene glycol, Tripropylene glycol and other aliphatic diols; Hydroquinone, resorcinol, catechol, naphthalenediol, biphenol, bisphenol A, hisphenol F , Tetramethylbiphenol, these ethylene oxide extenders, aromatic polyvalent phenols such as hydrogenated alicyclic group, and the like can be exemplified. Among them, it is presumed that the smaller the number of carbon atoms between oxygen atoms, the less flexible the molecular chain is and the more difficult it is for oxygen to permeate. Therefore, ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedim Methanol is preferred, and ethylene glycol is more preferred.

The polyester polyol (A2) having a polymerizable carbon-carbon double bond is a reaction product of a polyester polyol (a2) having a hydroxyl group and a carboxylic acid having a polymerizable double bond or a carboxylic acid anhydride. You may. Examples of the carboxylic acid having a polymerizable double bond or an acid anhydride thereof include a carboxylic acid having a polymerizable double bond such as maleic acid, maleic anhydride, or fumaric acid, and unsaturated fatty acids such as oleic acid and sorbic acid. Can be mentioned. The polyester polyol (a2) preferably has three or more hydroxyl groups. When the polyester polyol (a2) has two or less hydroxyl groups, the number of hydroxyl groups contained in the polyester polyol (A2) is 0 to 1, and molecular elongation is unlikely to occur during the reaction with the polyisocyanate composition (B) described later. As a result, the adhesive strength and the like may decrease.

The polyester polyol (A2) preferably has a double bond component ratio of 5 to 60% by mass. If it is less than 5% by mass, the number of cross-linking points between the polymerizable double bonds is reduced, and it becomes difficult to obtain gas barrier properties. If it exceeds 60% by mass, the number of cross-linking points increases, and the flexibility of the cured coating film may decrease, making it difficult to obtain adhesive strength. In the present specification, the double bond component ratio in the polyester polyol (A2) is calculated using the following formula (a). In the following formula, the monomer refers to a polyvalent carboxylic acid and a polyhydric alcohol used in the synthesis of polyester polyol (A2).

Further, as the polyester polyol (A2), a drying oil or a semi-drying oil can be mentioned. Examples of the drying oil or the semi-drying oil include known and commonly used drying oils and semi-drying oils having a carbon-carbon double bond.

The polyester polyol (A3) having a glycerol skeleton has a glycerol skeleton represented by the following general formula (1).

(In the general formula (1), R ₁ to R ₃ are independently hydrogen atoms or the following general formula (2). However, at least one of _{R 1} to R _{3 is the following general formula (2).} ) Represents a group represented by.)

(In the general formula (2), n represents an integer of 1 to 5, and X is a 1,2-phenylene group, a 1,2-naphthylene group, a 2,3-naphthylene group which may have a substituent. It represents an arylene group selected from the group consisting of a 2,3-anthraquinonediyl group and a 2,3-anthracendyl group, and Y represents an alkylene group having 2 to 6 carbon atoms.)

Polyester polyol (A3) is _a compound any one of R 1, _{R 2} and _{R 3} is a group represented by the general formula _(2), R 1, _{R 2} and one of _{R 3} 2 two generally formula A mixture of two or more compounds of the compound which is the group represented by (2) and the compound which is the group in which all of _{R 1} , R ₂ and R _{3 are represented by the general formula (2).} May be. It is more preferable that all of R ₁ to R ₃ are groups represented by the general formula (2).

In the general formula (2), when X is substituted with a substituent, it may be substituted with one or more substituents, and the substituent is any carbon atom on X different from the free radical. Is bound to. Examples of the substituent include a chloro group, a bromo group, a methyl group, an ethyl group, an i-propyl group, a hydroxyl group, a methoxy group, an ethoxy group, a phenoxy group, a methylthio group, a phenylthio group, a cyano group, a nitro group and an amino group. Examples thereof include a phthalimide group, a carboxyl group, a carbamoyl group, an N-ethylcarbamoyl group, a phenyl group or a naphthyl group.

Specific examples of Y in the general formula (2) include an ethylene group, a propylene group, a butylene group, a neopentylene group, a 1,5-pentylene group, a 3-methyl-1,5-pentylene group, and a 1,6-hexylene group. It is an alkylene group having 2 to 6 carbon atoms, such as a methylpentylene group and a dimethylbutylene group. A propylene group and an ethylene group are preferable, and an ethylene group is more preferable.

The polyester polyol (A3) is obtained by reacting glycerol, an aromatic polyvalent carboxylic acid in which the carboxylic acid is substituted at the ortho position or an acid anhydride thereof, and a polyhydric alcohol as essential components.

Examples of the aromatic polyvalent carboxylic acid in which the carboxylic acid is substituted at the ortho position or an acid anhydride thereof include orthophthalic acid or an acid anhydride thereof, naphthalene 2,3-dicarboxylic acid or an acid anhydride thereof, naphthalene 1,2-dicarboxylic acid. Examples thereof include an acid or an acid anhydride thereof, anthraquinone 2,3-dicarboxylic acid or an acid anhydride thereof, and 2,3-anthracenecarboxylic acid or an acid anhydride thereof. These compounds may have a substituent on any carbon atom of the aromatic ring. Examples of the substituent include a chloro group, a bromo group, a methyl group, an ethyl group, an i-propyl group, a hydroxyl group, a methoxy group, an ethoxy group, a phenoxy group, a methylthio group, a phenylthio group, a cyano group, a nitro group and an amino group. Examples thereof include a phthalimide group, a carboxyl group, a carbamoyl group, an N-ethylcarbamoyl group, a phenyl group or a naphthyl group.

As the polyvalent carboxylic acid, another polyvalent carboxylic acid may be copolymerized as long as the effect of the present invention is not impaired. Specifically, aliphatic polyvalent carboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, and dodecanediocarboxylic acid; unsaturated bond-containing polyvalent carboxylic acids such as maleic anhydride, maleic acid, and fumaric acid; , 3-Cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and other alicyclic polyvalent carboxylic acids; terephthalic acid, isophthalic acid, pyromellitic acid, trimellitic acid, 1,4-naphthalenedicarboxylic acid, 2,5 -Naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, diphenic acid and its acid anhydride, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid and these dicarboxylic acids Examples thereof include aromatic polyvalent carboxylic acids such as acid anhydrides or ester-forming derivatives, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid and ester-forming derivatives of these dihydroxycarboxylic acids. Species or two or more species can be used together. Of these, succinic acid, 1,3-cyclopentanedicarboxylic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalic acid, and diphenic acid are preferable.

Examples of the polyhydric alcohol include an alkylene diol having 2 to 6 carbon atoms. For example, diols such as ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol, and dimethylbutanediol. Can be exemplified.

Further, a polyhydric alcohol other than glycerol and an alkylene diol having 2 to 6 carbon atoms may be copolymerized as long as the effect of the present invention is not impaired. Specifically, aliphatic polyhydric alcohols such as erythritol, pentaerythol, dipentaerythritol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetraethylene glycol and tripropylene glycol, cyclohexanedi. Aliphatic polyhydric alcohols such as methanol and tricyclodecanedimethanol, aromatic polyhydric phenols such as hydroquinone, resorcinol, catechol, naphthalenediol, biphenol, bisphenol A, hisphenol F, tetramethylbiphenol, or ethylene oxide thereof. Elongates and hydrolyzed aliphatic ring groups can be exemplified.

When the polyol composition (A) contains the polyester polyol (A3) as a main component, the content of the glycerol residue contained in the polyester polyol (A3) in the solid content of the gas barrier adhesive is 5% by mass or more. preferable. The glycerol residue refers to a residue (C ₃ H ₅ O ₃ _{= 89.07) excluding R 1} to R ₃ in the general formula (1), and is calculated using the following formula (b).

In the above formula (b), P refers to the polyester polyol (A3). The resin solid content mass of the gas barrier adhesive is determined from the total mass of the polyol composition (A) and the polyisocyanate composition (B) to be used, the diluting solvent (in the case of the dry lamination adhesive), and the polyisocyanate composition (B). The mass shall be the mass excluding the mass of volatile components and inorganic components contained in.

The polyester polyol (A4) obtained by polycondensing an ortho-oriented polyvalent carboxylic acid and a polyhydric alcohol is a polyvalent carboxylic acid containing at least one orthophthalic acid and its acid anhydride, ethylene glycol, and propylene. It consists of a polyhydric alcohol containing at least one selected from the group consisting of glycols, butylene glycols, neopentyl glycols, and cyclohexanedimethanol. In particular, a polyester polyol in which the usage rate of the orthophthalic acid and its acid anhydride with respect to the total amount of the polyvalent carboxylic acid is 70 to 100% by mass is preferable.

The polyvalent carboxylic acid requires either orthophthalic acid or an acid anhydride thereof, but other polyvalent carboxylic acids may be copolymerized as long as the effects of the present invention are not impaired. Specifically, the aliphatic polyvalent carboxylic acid includes succinic acid, adipic acid, azelaic acid, sebacic acid, dodecandicarboxylic acid and the like, and the unsaturated bond-containing polyvalent carboxylic acid includes maleic anhydride and maleic acid. Fumaric acid and the like, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and the like as the alicyclic polyvalent carboxylic acid, and terephthalic acid, isophthalic acid and frangicarboxylic acid as the aromatic polyvalent carboxylic acid. Acid, pyromellitic acid, trimellitic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane -P, p'-dicarboxylic acids and acid anhydrides or ester-forming derivatives of these dicarboxylic acids; p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid and ester-forming derivatives of these dihydroxycarboxylic acids, etc. The polybasic acids of can be used alone or in admixture of two or more. Of these, succinic acid, 1,3-cyclopentanedicarboxylic acid, and isophthalic acid are preferable.

The polyhydric alcohol includes at least one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol, but other polyhydric alcohols can be used as long as the effects of the present invention are not impaired. It may be copolymerized. Specifically, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetra. Aliphatic diols such as ethylene glycol, dipropylene glycol and tripropylene glycol; hydroquinone, resorcinol, catechol, naphthalenediol, biphenol, bisphenol A, hisphenol F, tetramethylbiphenol and their ethylene oxide extensions, hydrogenated Aromatic polyhydric phenols such as alicyclics can be exemplified.

The polyester polyol (A5) having an isocyanul ring is represented by the following general formula (3).

(In the general formula (3), R ₁ to R ₃ are independently _{represented by-(CH 2} ) _n1 -OH (where _n1 represents an integer of 2 to 4) or the following general formula (4). However _{, at least one of R 1} , R ₂ and R ₃ is a group represented by the general formula (4).)

(In the general formula (4), n2 represents an integer of 2 to 4, n3 represents an integer of 1 to 5, and X is a 1,2-phenylene group, a 1,2-naphthylene group, and a 2,3-naphthylene group. , 2,3-Anthraquinonediyl group, and 2,3-Anthracendyl group selected from the group and may have a substituent, Y represents an alkylene group having 2 to 6 carbon atoms. Represent.)

Polyester polyol (A5) _includes a compound any one of R 1, _{R 2} and _{R 3} is a group represented by the general formula _(4), R 1, _{R 2} and one of _{R 3} 2 two generally formula A mixture of two or more compounds of the compound which is the group represented by (4) and the compound which is the group in which all of _{R 1} , R ₂ and R _{3 are represented by the general formula (4).} May be. It is more preferable that all of R ₁ to R ₃ are groups represented by the general formula (4).

In the general formula (3), the _{alkylene group represented by − (CH2) n1} − may be linear or branched. Of these, n1 is preferably 2 or 3, and most preferably 2.

In the general formula (4), when X is substituted with a substituent, it may be substituted with one or more substituents, and the substituent is any carbon atom on X different from the free radical. Is bound to. Examples of the substituent include a chloro group, a bromo group, a methyl group, an ethyl group, an i-propyl group, a hydroxyl group, a methoxy group, an ethoxy group, a phenoxy group, a methylthio group, a phenylthio group, a cyano group, a nitro group and an amino group. Examples thereof include a phthalimide group, a carboxyl group, a carbamoyl group, an N-ethylcarbamoyl group, a phenyl group or a naphthyl group.

As the substituent of X, a hydroxyl group, a cyano group, a nitro group, an amino group, a phthalimide group, a carbamoyl group, an N-ethylcarbamoyl group and a phenyl group are preferable, and a hydroxyl group, a phenoxy group, a cyano group, a nitro group and a phthalimide group, A phenyl group is more preferred.

Specific examples of Y in the general formula (4) include an ethylene group, a propylene group, a butylene group, a neopentylene group, a 1,5-pentylene group, a 3-methyl-1,5-pentylene group, and a 1,6-hexylene group. It is an alkylene group having 2 to 6 carbon atoms, such as a methylpentylene group and a dimethylbutylene group. A propylene group and an ethylene group are preferable, and an ethylene group is more preferable.

The polyester polyol (A5) is obtained by reacting a triol having an isocyanul ring, an aromatic polyvalent carboxylic acid in which the carboxylic acid is substituted at the ortho position or an acid anhydride thereof, and a polyhydric alcohol as essential components.

Examples of triols having an isocyanuric ring include alkylene oxide adducts of isocyanuric acid such as 1,3,5-tris (2-hydroxyethyl) isocyanuric acid and 1,3,5-tris (2-hydroxypropyl) isocyanuric acid. And so on.

Examples of the aromatic polyvalent carboxylic acid in which the carboxylic acid is substituted at the ortho position or its acid anhydride include orthophthalic acid or its acid anhydride, naphthalene 2,3-dicarboxylic acid or its acid anhydride, and naphthalene 1,2-dicarboxylic acid. Examples thereof include an acid or an acid anhydride thereof, anthraquinone 2,3-dicarboxylic acid or an acid anhydride thereof, and 2,3-anthracenecarboxylic acid or an acid anhydride thereof. These compounds may have a substituent on any carbon atom of the aromatic ring. Examples of the substituent include a chloro group, a bromo group, a methyl group, an ethyl group, an i-propyl group, a hydroxyl group, a methoxy group, an ethoxy group, a phenoxy group, a methylthio group, a phenylthio group, a cyano group, a nitro group and an amino group. Examples thereof include a phthalimide group, a carboxyl group, a carbamoyl group, an N-ethylcarbamoyl group, a phenyl group or a naphthyl group.

Polyhydric alcohols include alkylenediols having 2 to 6 carbon atoms, specifically ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, Diols such as 1,6-hexanediol, methylpentanediol, and dimethylbutanediol can be exemplified.

Among them, 1,3,5-tris (2-hydroxyethyl) isocyanuric acid or 1,3,5-tris (2-hydroxypropyl) isocyanuric acid is used as the triol compound having an isocyanul ring, and the carboxylic acid is in the ortho position. A polyester polyol (A5) having an isocyanul ring using an aromatic polyvalent carboxylic acid substituted with or using orthophthalic anhydride as the acid anhydride and ethylene glycol as the polyhydric alcohol has improved gas barrier properties and adhesiveness. Excellent and preferable.

The isocyanul ring is highly polar and does not form hydrogen bonds. Generally, as a method for improving adhesiveness, a method of blending highly polar functional groups such as a hydroxyl group, a urethane bond, a ureido bond, and an amide bond is known, and a resin having these bonds forms an intermolecular hydrogen bond. It is easy and may impair the solubility in solvents such as ethyl acetate and 2-butanone, which are often used for solvent-based adhesives, but polyester resins having an isocyanul ring do not impair the solubility, so it is easy. It can be diluted.

Further, since the isocyanul ring is trifunctional, a polyester polyol compound having the isocyanul ring as the center of the resin skeleton and a polyester skeleton having a specific structure in the branched chain can obtain a high crosslink density. It is presumed that by increasing the crosslink density, the gap through which a gas such as oxygen passes can be reduced. As described above, it is presumed that the isocyanul ring has high polarity and high crosslink density without forming an intermolecular hydrogen bond, so that gas barrier properties and adhesiveness can be ensured.

From this point of view, when the polyol composition (A) contains the polyester polyol (A5) as a main component, the content of the isocyanuric ring contained in the polyester polyol (A5) in the solid content of the gas barrier adhesive is 5% by mass. The above is preferable. The isocyanul ring refers to the residue (C ₃ N ₃ O ₃ _{= 126.05) excluding R 1} to R ₃ in the general formula (3), and is calculated using the following formula (b).

In the above formula (c), P refers to the polyester polyol (A5). The resin solid content mass of the gas barrier adhesive is determined from the total mass of the polyol composition (A) and the polyisocyanate composition (B) to be used, the diluting solvent (in the case of the dry lamination adhesive), and the polyisocyanate composition (B). The mass shall be the mass excluding the mass of volatile components and inorganic components contained in.

The hydroxyl value of the polyester polyol is preferably 20 mgKOH / g or more and 250 mgKOH / g or less. When the hydroxyl value is smaller than 20 mgKOH / g, the viscosity of the polyol composition (A) becomes high because the molecular weight is too large, and good coating suitability cannot be obtained. When the hydroxyl value exceeds 250 mgKOH / g, the molecular weight is too small and the crosslink density of the cured coating film becomes too high, so that good adhesive strength cannot be obtained.

When the polyester polyol has an acid group, the acid value is preferably 200 mgKOH / g or less. When the acid value exceeds 200 mgKOH / g, the reaction between the polyol composition (A) and the polyisocyanate composition (B) becomes too fast, and good coating suitability cannot be obtained. The lower limit of the acid value of the polyester polyol is not particularly limited, but as an example, it is 20 mgKOH / g or more. When the acid value is 20 mgKOH / g or more, good gas barrier properties and initial cohesive force can be obtained by intermolecular interaction. The hydroxyl value of the polyester polyol can be measured by the hydroxyl value measuring method described in JIS-K0070, and the acid value can be measured by the acid value measuring method described in JIS-K0070.

It is particularly preferable that the number average molecular weight of the polyester polyol as described above is 300 to 5000 because a crosslink density having an excellent balance between adhesiveness and gas barrier property can be obtained. More preferably, the number average molecular weight is 350 to 3000. If the molecular weight is less than 300, the cohesive force of the adhesive at the time of coating becomes too small, and there is a possibility that the film may be displaced during laminating or the bonded film may be lifted. On the other hand, if the molecular weight is higher than 5000, the viscosity at the time of coating becomes too high and coating cannot be performed, or the adhesiveness is low and laminating may not be possible. The number average molecular weight is calculated from the obtained hydroxyl value and the number of functional groups of the designed hydroxyl group.

The glass transition temperature of the polyester polyol is preferably −30 ° C. or higher and 80 ° C. or lower, more preferably 0 ° C. or higher and 60 ° C. or lower, and further preferably 25 ° C. or higher and 60 ° C. or lower. If the glass transition temperature exceeds 80 ° C., the flexibility of the polyester polyol at around room temperature is low, so that the adhesion to the substrate is poor and the adhesiveness may be lowered. On the other hand, if the temperature is lower than -30 ° C, the molecular motion of the polyester polyol at around room temperature is intense, so that sufficient gas barrier properties may not be obtained.

The polyester polyol may be a polyester polyurethane polyol having a number average molecular weight of 1000 to 15000 by urethane elongation of polyester polyols (A1) to (A5) by reaction with a diisocyanate compound. Since the urethane-extended polyester polyol has a molecular weight component of a certain level or more and a urethane bond, it has excellent gas barrier properties, excellent initial cohesive force, and is excellent as an adhesive for laminating.

The polyisocyanate composition (B), which is a component of a two-component adhesive having a gas barrier property, contains an isocyanate compound. As the isocyanate compound, conventionally known compounds can be used without particular limitation, and tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydride diphenylmethane diisocyanate, xylylene diisocyanate, hydride xylylene diisocyanate, isophorone diisocyanate or Dimeric and trimeric of these isocyanate compounds, and excess amounts of these isocyanate compounds, such as ethylene glycol, propylene glycol, metaxylylene alcohol, 1,3-bishydroxyethylbenzene, 1,4-bishydroxyethylbenzene. , Trimethylol propane, glycerol, pentaerythritol, erythritol, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine, metaxylylene diisocyanate and other low molecular weight active hydrogen compounds and their alkylene oxide adducts, various polyester resins, poly Examples thereof include an adduct obtained by reacting with a high molecular weight active hydrogen compound of ether polyols and polyamides. Polyester polyisocyanate obtained by reacting polyester polyols (A1) to (A5) with a diisocyanate compound in an excess ratio of hydroxyl groups and isocyanate groups may be used. These can be used alone or in combination of two or more.

Alternatively, blocked isocyanate may be used as the isocyanate compound. Examples of the isocyanate blocking agent include phenols such as phenol, thiophenol, methylthiophenol, ethylthiophenol, cresol, xylenol, resorcinol, nitrophenol, and chlorophenol, acetoxime, methylethylketooxime, cyclohexanone oxime, and methanol. Alcohols such as ethanol, propanol and butanol, halogen-substituted alcohols such as ethylene chlorohydrin and 1,3-dichloro-2-propanol, tertiary alcohols such as t-butanol and t-pentanol, ε- Examples include lactams such as caprolactam, δ-valerolactam, γ-butyrolactam and β-propyrrolactam, and other active methylene compounds such as aromatic amines, imides, acetylacetone, acetoacetic acid ester and malonic acid ethyl ester. , Mercaptans, imines, ureas, diaryl compounds, sodium bicarbonate and the like. The blocked isocyanate is obtained by subjecting the above-mentioned isocyanate compound and an isocyanate blocking agent to an addition reaction by an appropriate method known and commonly used.

Of these, xylylene diisocyanate, hydrogenated xylylene diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate are preferable because good gas barrier properties can be obtained, and isocyanate compounds having a metaxylene skeleton such as metaxylylene diisocyanate and metahydrogenated xylylene diisocyanate are preferable. Is more preferable to use.

Examples of the isocyanate compound having a metaxylene skeleton include a trimer of xylene diisocyanate, a burette compound synthesized by reaction with an amine, and an adduct compound formed by reacting with an alcohol. When the adhesive is a solvent type, it is preferable to use an adduct body because the solubility in the organic solvent used for the solvent type adhesive is better than that of the trimer body and the burette body. As the adduct, an adduct formed by reacting with an alcohol appropriately selected from the above low molecular weight active hydrogen compounds can be used, and among them, ethylene oxide adducts of trimethylolpropane, glycerol, triethanolamine, and metaxylylenediamine can be used. An adduct body with an object is preferable.

Further, when a composition containing a polyester polyol having a carboxylic acid group remaining like the polyester polyol (A1) is used as the polyol composition (A), the polyisocyanate composition (B) contains an epoxy compound. You may be. Examples of epoxy compounds include diglycidyl ether of bisphenol A and its oligomer, diglycidyl ether of bisphenol A and its oligomer, orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, and p-oxybenzoic acid di. Glycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipate diglycidyl ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1 , 4-Butandiol diglycidyl ether, 1,6-hexanediol diglycidyl ether and polyalkylene glycol diglycidyl ethers, trimeric acid triglycidyl ester, triglycidyl isocyanurate, 1,4-diglycidyloxybenzene, diglycidyl Examples thereof include propylene urea, glycerol triglycidyl ether, trimethylol ethane triglycidyl ether, trimethylol propane triglycidyl ether, pentaerythritol tetraglycidyl ether, and triglycidyl ether as a glycerol alkylene oxide adduct.

When an epoxy compound is used, a widely known epoxy curing accelerator may be appropriately added for the purpose of accelerating curing as long as the object of the present invention is not impaired.

When a composition containing a polyol having a polymerizable carbon-carbon double bond such as the polyester polyol (A2) is used as the polyol composition (A), in order to promote the polymerization of the carbon-carbon double bond, A known polymerization catalyst can be used in combination, and a transition metal complex is mentioned as an example. The transition metal complex is not particularly limited as long as it is a compound having an ability to oxidatively polymerize a polymerizable double bond. For example, metals such as cobalt, manganese, lead, calcium, cerium, zirconium, zinc, iron, copper, octyl acid, naphthenic acid, neodecanoic acid, stearic acid, resin acid, tall oil fatty acid, tung oil fatty acid, linseed oil fatty acid, Salts with soybean oil fatty acids and the like can be used. The blending amount of the transition metal complex is preferably 0 to 10 parts by mass, more preferably 0 to 3 parts by mass with respect to the resin solid content contained in the polyol composition (A).

The polyol composition (A) and the polyisocyanate composition (B) have an equivalent ratio of the hydroxyl group contained in the polyol composition (A) to the isocyanate group contained in the polyisocyanate composition (B) of 1/0. It is preferably blended so as to be 5 to 1/10, and more preferably to be blended so as to be 1/1 to 1/5. When the isocyanate compound is excessive, the excess isocyanate compound remaining in the cured coating film of the adhesive may bleed out from the adhesive layer. On the other hand, if the reactive functional groups contained in the polyisocyanate composition (B) are insufficient, the adhesive strength may be insufficient.

Various additives may be added to the gas barrier adhesive as long as the adhesiveness and gas barrier properties are not impaired.

Inorganic filler may be used as such an additive. Examples of the inorganic filler include silica, alumina, aluminum flakes, glass flakes and the like. In particular, it is preferable to use a plate-shaped inorganic compound as the inorganic filler because the adhesive strength, gas barrier property, light-shielding property and the like are improved. Plate-like inorganic compounds include hydrous silicates (phyllocate minerals, etc.), kaolinite-serpentine clay minerals (haloisite, kaolinite, enderite, dikite, nacrite, etc., antigolite, chrysotile, etc.), pyrophyllium. Light-Tark (pyrophyllite, talc, kerolai, etc.), smectite clay minerals (montmorillonite, biderite, nontronite, saponite, hectrite, saconite, stivuncite, etc.), vermiculite clay minerals (vermiculite, etc.), mica or Mica clay minerals (white mica, gold mica, etc., margarite, tetracylic mica, teniolite, etc.), green mudstones (cookate, sudoite, clinochloa, chamosite, nimite, etc.), hydrotalcite, plate sulfate Examples thereof include barium, boehmite and aluminum polyphosphate. These minerals may be natural clay minerals or synthetic clay minerals. The plate-like inorganic compound may be used alone or in combination of two or more.

The plate-like inorganic compound may be an ionic compound having an electric charge between layers, or a nonionic compound having no electric charge. The presence or absence of electric charge between layers does not directly affect the gas barrier property of the adhesive layer. However, ionic plate-like inorganic compounds and inorganic compounds that have swelling properties with respect to water are inferior in dispersibility in solvent-type adhesives, and when the amount added is increased, they become thicker with the adhesives or become chysole. As a result, the coating suitability may decrease. Therefore, the plate-like inorganic compound is preferably nonionic without interlayer electrification.

The average particle size of the plate-shaped inorganic compound is not particularly limited, but as an example, it is preferably 0.1 μm or more, and more preferably 1 μm or more. If it is smaller than 0.1 μm, the detour route of oxygen molecules will not be long, and improvement of gas barrier property cannot be expected sufficiently. The upper limit of the average particle size is not particularly limited, but if the particle size is too large, defects such as streaks may occur on the coated surface depending on the coating method. Therefore, as an example, the average particle size is preferably 100 μm or less, and preferably 20 μm or less. In the present specification, the average particle size of the plate-shaped inorganic compound means the particle size that appears most frequently when the particle size distribution of the plate-shaped inorganic compound is measured by a light scattering type measuring device.

The aspect ratio of the plate-like inorganic compound is preferably high in order to improve the gas barrier property due to the maze effect of oxygen. Specifically, it is preferably 3 or more, more preferably 10 or more, and most preferably 40 or more.

The blending amount of the plate-shaped inorganic compound is arbitrary, but as an example, when the total solid content of the polyol composition (A), the polyisocyanate composition (B), and the plate-shaped inorganic compound is 100 mass, the plate-shaped inorganic compound is formed. The blending amount of the inorganic compound is 5 to 50 parts by mass.

The gas barrier adhesive may contain an adhesion promoter. Examples of the adhesion accelerator include silane coupling agents such as hydrolyzable alkoxysilane compounds, titanate-based coupling agents, aluminum-based coupling agents, epoxy resins and the like. Silane coupling agents and titanate-based coupling agents can be expected to have the effect of improving the adhesiveness to various film materials.

When the gas barrier adhesive layer needs to be acid resistant, the gas barrier adhesive may contain a known acid anhydride. Examples of the acid anhydride include phthalic acid anhydride, succinic acid anhydride, het acid anhydride, hymic acid anhydride, maleic acid anhydride, tetrahydrophthalic acid anhydride, hexahydraphthalic acid anhydride, and tetrapromphthalic acid. Anhydride, tetrachlorphthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenotetracarboxylic acid anhydride, 2,3,6,7-naphthalintetracarboxylic acid dianhydride, 5- (2) , 5-Oxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, maleic anhydride copolymer, and the like.

If necessary, a compound having an oxygen trapping function or the like may be further added. Examples of the compound having an oxygen trapping function include low molecular weight organic compounds that react with oxygen such as hindered phenols, vitamin C, vitamin E, organic phosphorus compounds, gallic acid, and pyrogallol, cobalt, manganese, nickel, iron, and the like. Examples thereof include transition metal compounds such as copper.

In order to improve the adhesiveness to various film materials immediately after application, a tackifier such as xylene resin, terpene resin, phenol resin, rosin resin may be added as needed. When these are added, the blending amount thereof is preferably in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the total solid content of the polyol composition (A) and the polyisocyanate composition (B).

When the polyol composition (A) contains a polyester polyol (A2), active energy rays can also be used as a method for reacting the polymerizable carbon-carbon double bond. A known technique can be used as the active energy ray, and it can be cured by irradiating it with ionizing radiation such as an electron beam, ultraviolet rays, or γ rays. When curing with ultraviolet rays, a known ultraviolet irradiation device equipped with a high-pressure mercury lamp, an excimer lamp, a metal halide lamp, or the like can be used.

When curing by irradiating with ultraviolet rays, 0.1 to 20 parts by mass of a light (polymerization) initiator that generates radicals or the like by irradiation with ultraviolet rays is added to 100 parts by mass of polyester polyol (A2), if necessary. It is preferable to add to some extent.

Radical-generating light (polymerization) initiators include hydrogen abstraction types such as benzyl, benzophenone, Michler's ketone, 2-chlorothioxanthone, and 2,4-diethylthioxanthone, and benzoin ethyl ether, diethoxyacetophenone, benzylmethylketal, and hydroxy. Examples thereof include photocleavable types such as cyclohexylphenyl ketone and 2-hydroxy-2-methylphenyl ketone. Among these, one or a plurality of them can be used alone or in combination.

In addition, the gas barrier adhesive may contain stabilizers (antioxidants, heat stabilizers, UV absorbers, etc.), plasticizers, antistatic agents, lubricants, blocking inhibitors, colorants, crystal nucleating agents, and the like. .. These various additives may be added to either or both of the polyol composition (A) and the polyisocyanate composition (B) in advance, or the polyol composition (A) and the polyisocyanate composition ( It may be added when mixing with B).

The gas barrier adhesive used in the present invention may be in either a solvent type or a solventless type. In the present specification, the solvent-based adhesive is a method in which an adhesive is applied to a base material, then heated in an oven or the like to volatilize the organic solvent in the coating film, and then bonded to another base material, so-called dry. A form used in the laminating method. Examples of the solvent used include toluene, xylene, methylene chloride, tetrahydrofuran, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, acetone, methyl ethyl ketone (MEK), cyclohexanone, toluol, xylol, n-hexane, cyclohexane and the like. Can be mentioned. Either one or both of the polyol composition (A) and the polyisocyanate composition (B) contains the above-mentioned organic solvent. In the case of the solvent type, the solvent used as the reaction medium in the production of the constituent components of the polyol composition (A) or the polyisocyanate composition (B) may be further used as a diluent in coating.

The solvent-free adhesive is used in the so-called non-solvent laminating method, which is a method in which an adhesive is applied to a base material and then bonded to another base material without the process of heating in an oven or the like to volatilize the solvent. Refers to the form to be used. Neither the polyol composition (A) nor the polyisocyanate composition (B) is substantially free of the organic solvents described above. The constituent components of the polyol composition (A) or the polyisocyanate composition (B) and the organic solvent used as the reaction medium in the production of the raw material thereof could not be completely removed, and the polyol composition (A) or the polyisocyanate composition (A) or the polyisocyanate composition ( If a small amount of organic solvent remains in B), it is understood that the organic solvent is substantially not contained. Further, when the polyol composition (A) contains a low molecular weight alcohol, the low molecular weight alcohol reacts with the polyisocyanate composition (B) and becomes a part of the coating film, so that it is not necessary to volatilize after coating. Therefore, such a form is also treated as a solvent-free adhesive.

(Sealant layer)
The laminate of the present invention may have a sealant layer on the gas barrier adhesive layer. The sealant layer is a heat-sealing resin layer that can be melted by heat and fused to each other. Suitable resins for the sealant layer include polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene- ( Olefin resins such as meta) acrylate copolymer, ethylene- (meth) ethyl acrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, polyethylene or polypropylene are used as acrylic acid, methacrylic acid, maleic anhydride, etc. Fumaric acid and other modified olefin resins modified with unsaturated carboxylic acid, ternary copolymer of ethylene- (meth) acrylic acid ester-unsaturated carboxylic acid, cyclic polyolefin, cyclic olefin copolymer, polyethylene terephthalate (PET), polyacrylonitrile (PAN) and the like. A resin film, sheet, or other coating film made of one or more of these resins can be used as the sealant layer.

As the film to be the sealant layer, any unstretched, uniaxially stretched, or biaxially stretched film can be used.

The stretched film stretched in the biaxial direction is, for example, vertically stretched 2 to 4 times by a roll stretching machine at 50 to 100 ° C., and further laterally stretched 3 to 5 times by a tenter stretching machine in an atmosphere of 90 to 150 ° C. Subsequently, it is obtained by heat treatment with a tenter stretching machine in an atmosphere of 100 to 240 ° C. Alternatively, simultaneous biaxial stretching and sequential biaxial stretching may be used.

An easily peelable sealant film (easy peel film) may be used for the sealant layer. As the easily peelable sealant film, any of an interface peeling type, a cohesive peeling type, and an interlayer peeling type can be applied, and can be appropriately selected according to the type of packaging material and the required characteristics described later. The index of easy peelability is appropriately set according to the type of packaging material and the required characteristics, and as an example, the seal strength is 2 to 20 N / 15 mm. For example, easy peelability can be exhibited by a phase-separated polymer blend in which polypropylene is combined with high-density polyethylene, low-density polyethylene, an ethylene-vinyl acetate copolymer, or the like.

The film thickness of the sealant layer can be arbitrarily selected, but when applied to a packaging material described later, for example, it is selected in the range of 5 to 500 μm. It is more preferably 10 to 250 μm, and even more preferably 15 to 100 μm. If it is less than 5 μm, sufficient laminating strength as a packaging material cannot be obtained, and there is a risk that piercing resistance and the like will be lowered. If it exceeds 250 μm, the cost will increase and the film will become hard, resulting in reduced workability.

(Print layer)
The laminate of the present invention may have a printed layer, if necessary. The position of the printing layer is arbitrary, but as an example, gas barrier property is provided on the surface opposite to the gas barrier adhesive layer of the base material, or between the gas barrier coating layer and the gas barrier adhesive layer. It is provided in contact with the coating layer. The printing layer is formed by various printing inks such as gravure ink, flexo ink, offset ink, stencil ink, and inkjet ink by a general printing method conventionally used for printing on a polymer film.

(Laminated body and other layers)
The laminate of the present invention may have other layers, if necessary. For example, a film may be arranged between the gas barrier adhesive layer and the sealant layer. As the film, the same film as that exemplified as the base material can be used. Uniaxial or biaxially stretched polyester film such as polyethylene terephthalate and polyethylene naphthalate, uniaxial or biaxially stretched polyamide film such as nylon 6, nylon 66 and MXD6 (polymethoxylylen adipamide), biaxially stretched polypropylene film and the like. It can be preferably used.

When a film is arranged between the gas barrier adhesive layer and the sealant layer, the film and the sealant layer may be bonded to each other via an adhesive. The adhesive used at this time may or may not be the gas barrier adhesive described above. The film may be bonded to the base material via a gas barrier adhesive layer, or another layer may be arranged between the film and the gas barrier adhesive layer.

(Manufacturing method of laminated body)
The laminate of the present invention is obtained by laminating a base material provided with an aluminum oxide layer and a gas barrier coating layer and a sealant layer by a dry laminating method or a non-solvent laminating method using a gas barrier adhesive. .. The laminated laminate has excellent gas barrier properties and can be used as a gas barrier laminate.

The method for forming the gas barrier coating layer is not particularly limited, and the spray method, spin coating method, dip method, roll coating method, blade coating method, doctor roll method, doctor blade method, curtain coating method, slit coating method, etc. Examples include a screen printing method and an inkjet method. After coating, the organic solvent is volatilized by heating in an oven or the like.

When the gas barrier adhesive is a solvent type, the gas barrier adhesive is applied to either the base material or the sealant layer using a roll such as a gravure roll, and the organic solvent is volatilized by heating in an oven or the like. , The other is bonded to obtain the laminate of the present invention. It is preferable to perform an aging treatment after laminating. The aging temperature is preferably room temperature to 80 ° C., and the aging time is preferably 12 to 240 hours.

When the gas barrier adhesive is a solvent-free type, a gas barrier adhesive that has been preheated to about 40 ° C. to 100 ° C. is applied to either the base material or the sealant layer using a roll such as a gravure roll. After that, the other is immediately bonded to obtain the laminate of the present invention. It is preferable to perform an aging treatment after laminating. The aging temperature is preferably room temperature to 70 ° C., and the aging time is preferably 6 to 240 hours.

The amount of the gas barrier adhesive applied is adjusted as appropriate. In the case of the solvent type, as an example, the solid content is adjusted to be ^{1 g / m 2} or more and 10 g / m ² or less, preferably 1 g / m ² or more and 5 g / m ^{2 or less.} In the case of the solvent-free type, the amount of the adhesive applied is, for example, 1 g / m ² or more and 10 g / m ² or less, preferably 1 g / m ² or more and 5 g / m ² or less.

<Packaging material>
The laminate of the present invention can be used as a multi-layer packaging material for the purpose of protecting foods, pharmaceuticals and the like. When used as a multi-layer packaging material, its layer structure may change depending on the contents, usage environment, and usage pattern.

The packaging material of the present invention is obtained by using the laminate of the present invention, laminating the surfaces of the sealant films of the laminate facing each other, and then heat-sealing the peripheral end portions thereof. As a bag-making method, the laminate of the present invention is bent or overlapped so that the inner layer surface (the surface of the sealant film) faces each other, and the peripheral end thereof is, for example, a side seal type or a two-way seal type. Three-way seal type, four-way seal type, envelope-attached seal type, gassho-attached seal type (vertical pillow, horizontal pillow), fold-attached seal type, flat-bottom seal type, square-bottom seal type, gusset type, and other heat-seal types There is a method of heat-sealing. The packaging material of the present invention can take various forms depending on the contents, the environment of use, and the form of use. Free-standing packaging materials (standing pouches), etc. are also possible. As a heat sealing method, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, and an ultrasonic seal can be used.

After filling the packaging material of the present invention with the contents from the opening, the opening is heat-sealed to manufacture a product using the packaging material of the present invention. The contents to be filled include rice confectionery, bean confectionery, nuts, biscuits / cookies, wafer confectionery, marshmallows, pies, half-baked cakes, candy, snack confectionery and other confectionery, bread, snack noodles, instant noodles, dried noodles, pasta. , Sterile packaged rice, elephant, porridge, packaged rice, staples such as cereal foods, pickles, boiled beans, natto, miso, frozen tofu, tofu, licked mushrooms, konjac, processed wild vegetables, jams, peanut cream, salads, frozen Processed agricultural products such as vegetables and processed potatoes, hams, bacon, sausages, processed chicken products, processed livestock products such as confectionery, fish meat hams and sausages, marine products, kamaboko, glue, boiled vegetables, sardines, salted spicy, Processed marine products such as smoked salmon and spicy cod roe, peaches, tangerines, pineapples, apples, pears, cherries and other fruit meats, corn, asparagus, mushrooms, onions, carrots, radishes, potatoes and other vegetables, hamburgers, meat Cooked foods such as balls, fried fish, gyoza, croquette and other frozen side dishes, chilled side dishes, butter, margarine, cheese, cream, instant creamy powder, dairy products such as baby-prepared powdered milk, liquid seasonings, retorts Examples include foods such as curry and pet food. The packaging material of the present invention can also be used as a packaging material for cigarettes, disposable body warmers, pharmaceuticals such as infusion packs, cosmetics, and vacuum heat insulating materials.

(Types of gas components that can block permeation)
Examples of the gas that can be blocked by the resin composition of the present invention and the laminate containing the resin composition include oxygen, an inert gas such as carbon dioxide, nitrogen and argon, an alcohol component such as methanol, ethanol and propanol, and phenol. In addition to phenols such as cresol, aroma components composed of low molecular weight compounds such as soy sauce, sauce, miso, limonene, menthol, methyl salicylate, coffee, cocoa shampoo, and rinse can be exemplified.

<Packaging material and packaging material for heat sterilization>
Since the laminate of the present invention has excellent gas barrier properties, it can be suitably used as a packaging material that requires gas barrier properties. In particular, foods, daily necessities, electronic materials, medical materials, etc. require high barrier properties, so that the packaging material of the present invention can be preferably used.
Furthermore, since it is excellent in heat resistance and moisture heat resistance, it can be suitably used as a packaging material for heat sterilization such as boiling and retort.

The packaging material of the present invention may be a lid material using the laminate of the present invention.

The present invention will be described below with reference to examples, but the present invention is not limited to the examples. Unless otherwise specified, the unit is weight conversion.

Definition of terms: The molecular weight of a unit of polyacrylic acid (hereinafter sometimes abbreviated as PAA) is 72. Usually, one molecule of zinc oxide (molecular weight 81.4) (hereinafter, may be abbreviated as ZnO) contributes to the reaction and forms a salt with respect to two molecules of a unit unit of PAA (molecular weight 72 × 2). A formulation blended with PAA weight: ZnO weight = 144 / 82.4 = 100/57 is referred to as blending 1 equivalent of ZnO.

<How to prepare PAA solution>
(PAA adjustment example 1)
In a flask, PAA powder having a number average molecular weight of 9000 (Julimer AC-10P, manufactured by Toa Synthetic Co., Ltd.): 20 g was dissolved in isopropyl alcohol (manufactured by Kanto Chemical Co., Inc.): 980 g while stirring and boiling, and the solid content concentration was 2%. A PAA solution 1 having a molecular weight of 9000 was obtained.

(PAA adjustment example 2)
In a flask, PAA powder having a number average molecular weight of 250,000 (Julimer AC-10LHPK, manufactured by Toa Synthetic Co., Ltd.): 20 g of isopropyl alcohol (hereinafter sometimes abbreviated as IPA) manufactured by Kanto Chemical Co., Inc .: while stirring and boiling in 980 g. It was dissolved to obtain a PAA solution 2 having a molecular weight of 250,000 and having a solid content concentration of 2%.

(PAA adjustment example 3)
In a flask, 20 g of PAA powder having a number average molecular weight of 800,000 (Aqualic AS-58, manufactured by Nippon Catalyst Co., Ltd.) was dissolved in 980 g of isopropyl alcohol (manufactured by Kanto Chemical Co., Inc.) while stirring and boiling, and the solid content concentration was 2. A PAA solution 3 having a molecular weight of 800,000% was obtained.

<How to adjust ZnO dispersion>
(ZnO adjustment example 1)
Regarding the dispersion solution of ZnO, ZnO (manufactured by Sakai Chemical Industry Co., Ltd., FINEX-50): 200 g and IPA: 800 g are mixed and contained in a bead mill (manufactured by Kotobuki Co., Ltd .: Ultra Aspek Mill UAM-015). After dispersion treatment for 1 hour using zirconia beads having a diameter of 0.3 mm, the beads were sifted to obtain a ZnO solution having a solid content concentration of 20%. This solution was diluted with IPA to obtain an IPA dispersion of ZnO having a solid content concentration of 2%. The particle size of ZnO in this dispersion was 88 nm.

<How to adjust the coating agent for comparison>
2.7 parts of Takenate D-110N (manufactured by Mitsui Chemicals, Inc.) as a curing agent was mixed with 7.3 parts of a solution prepared by dissolving 30 parts of "Byron GK880" (manufactured by Toyobo) in 70 parts of methyl ethyl ketone, and further. 19 parts of methyl ethyl ketone was added to obtain a comparative coating agent having a solid content concentration of 10%.

<Adhesive adjustment example>
[Polycarbonate]
(EGoPA 0.9K) "Polycarbonate A1"
80.12 parts of ethylene glycol, 148.12 parts of phthalic anhydride, and 0.02 parts of titanium tetraisopropoxide were charged in a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a snider tube, and a condenser, and the temperature of the upper part of the rectification tube was increased. Was gradually heated so as not to exceed 100 ° C., and the internal temperature was maintained at 220 ° C. When the acid value became 1 mgKOH / g or less, the esterification reaction was terminated to obtain a polyester polyol "polyester A1" having a number average molecular weight of 900 and a hydroxyl value of 124.7 mgKOH / g.

(EGoPA / AA 0.5K) "Polycarbonate A2"
207.37 parts of phthalic anhydride, 184.0 parts of ethylene glycol, 87.68 parts of adipic acid and titanium tetraisopropoxide in a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a rectification tube, a water separator, etc. 0.014 parts were charged and gradually heated so that the temperature of the upper part of the rectification tube did not exceed 100 ° C. to maintain the internal temperature at 220 ° C. The esterification reaction was terminated when the acid value became 1 mgKOH / g or less to obtain a polyester polyol "polyester A2" having a number average molecular weight of about 500, a hydroxyl value of 224.4 mgKOH / g, and an acid value of 0.9 mgKOH / g.

(EGoPA / MA 0.6K) "Polycarbonate A3"
In a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a rectification tube, a water separator, etc., 98.1 parts of maleic anhydride, 78.5 parts of ethylene glycol and titanium tetraisopropoxide are added as a polyvalent carboxylic acid. An amount corresponding to 100 ppm with respect to the total amount with the valent alcohol was charged, and the internal temperature was maintained at 205 ° C. by gradually heating the rectification tube so that the upper temperature did not exceed 100 ° C. The esterification reaction was terminated when the acid value became 1 mgKOH / g or less to obtain a polyester polyol "polyester A3" having a number average molecular weight of about 600, a hydroxyl value of 182 mgKOH / g, and an acid value of 0.9 mgKOH / g.

(EGoPA / FDCA 0.5K) "Polycarbonate A4"
80.12 parts of ethylene glycol, 74.06 parts of phthalic anhydride, 78.05 of frangylcarboxylic acid and 0.02 parts of titanium tetraisopropoxide are charged in a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction pipe, a snider pipe, and a condenser. , The internal temperature was maintained at 220 ° C. by gradually heating so that the temperature of the upper part of the rectification tube did not exceed 100 ° C. The esterification reaction was terminated when the acid value became 1 mgKOH / g or less to obtain a polyester polyol "polyester A4" having a number average molecular weight of 500, a hydroxyl value of 220.4 mgKOH / g, and an acid value of 0.8 mgKOH / g.

(GLY (EGoPA) 3) "Polycarbonate A5"
92.09 parts of glycerol, 444.36 parts of phthalic anhydride, 186.21 parts of ethylene glycol, and 0.07 of titanium tetraisopropoxide in a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a snyder tube, and a condenser. The portion was charged and gradually heated so that the temperature of the upper part of the rectification tube did not exceed 100 ° C. to maintain the internal temperature at 220 ° C. The esterification reaction was terminated when the acid value became 1 mgKOH / g or less to obtain a polyester polyol "polyester A5" having a number average molecular weight of 668.60, a hydroxyl value of 250 mgKOH / g, and an acid value of 0.5 mgKOH / g.

(GLY (EGoPA) 3 + MICA) "Polycarbonate A6"
70 parts of "polypoly A5" was charged into a container equipped with a stirrer and heated and stirred at 90 ° C. to bring the polyol into a state of sufficiently maintaining fluidity. While stirring, 30 parts of HM6025 (manufactured by HENGHAO, natural mica / non-swellable, plate-shaped, average particle size 10 μm, aspect ratio 100 or more) was added, and the mixture was stirred at 90 ° C. until uniform. By cooling this, "polypoly A6" in which an inorganic compound was dispersed in "polyol A5" was obtained.

(EGoPA / AA 0.5K + MICA) "Polycarbonate A7"
70 parts of "polypoly A2" was charged into a container equipped with a stirrer and heated and stirred at 90 ° C. to bring the polyol into a state of sufficiently maintaining fluidity. While stirring, 30 parts of HM6025 (manufactured by HENGHAO, natural mica / non-swellable, plate-shaped, average particle size 10 μm, aspect ratio 100 or more) was added, and the mixture was stirred at 90 ° C. until uniform. By cooling this, "polypoly A7" in which an inorganic compound was dispersed in "polyol A2" was obtained.

(DEG / AA2.0K) "Polycarbonate A8"
125.33 parts of diethylene glycol, 146.14 parts of adipic acid, and 0.02 parts of titanium tetraisopropoxide were charged in a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a snider tube, and a condenser, and the temperature of the upper part of the rectification tube was increased. Was gradually heated so as not to exceed 100 ° C., and the internal temperature was maintained at 220 ° C. The esterification reaction was terminated when the acid value became 1 mgKOH / g or less to obtain a polyester polyol "polyester A8" having a number average molecular weight of 2000, a hydroxyl value of 56.1 mgKOH / g, and an acid value of 1.0 mgKOH / g.

(Preparation of polyisocyanate composition)
"Hardener B1"
A polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a snyder tube, and a condenser is charged with 80.12 parts of ethylene glycol, 148.12 parts of phthalic anhydride, and 0.02 parts of titanium tetraisopropoxide, and a rectification tube. The internal temperature was maintained at 220 ° C. by gradually heating so that the upper temperature did not exceed 100 ° C. When the acid value became 1 mgKOH / g or less, the esterification reaction was terminated to obtain a polyol intermediate having a number average molecular weight of 400. Next, 71.45 parts of xylylene diisocyanate, millionate MN (4,4'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate) were added to a reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a snider tube, a cooling condenser, and a dropping funnel. 46.26 parts of the mixture was added and stirred while heating at 70 ° C., and 73.82 parts of the polyol intermediate was added dropwise using a dropping funnel over 2 hours, and the mixture was further stirred for 4 hours to obtain polyisocyanate. "Hardener B1" was obtained. The NCO% measured according to JIS-K1603 was 15.1%.

"Hardener B2"
71.45 parts of xylylene diisocyanate, a mixture of 4,4'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate in a reaction vessel equipped with a stirrer, nitrogen gas introduction tube, snider tube, cooling condenser, and dropping funnel. ) 46.26 parts were added and stirred while heating at 70 ° C., 92.28 parts of "polyol A2" was added dropwise using a dropping funnel over 2 hours, and the mixture was further stirred for 4 hours to obtain "polyisocyanate". Hardener B2 ”was obtained. The NCO% measured according to JIS-K1603 was 15.1%.

"Hardener B3"
24.72 parts of ethylene glycol, 60.10 parts of diethylene glycol, 2.49 parts of neopentyl glycol, 125.3 parts of adipate and titanium tetraiso in a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a snyder tube, and a condenser. 0.02 part of propoxide was charged and gradually heated so that the temperature of the upper part of the rectification tube did not exceed 100 ° C. to maintain the internal temperature at 220 ° C. When the acid value became 1 mgKOH / g or less, the esterification reaction was terminated to obtain an intermediate. Put 83.45 parts of Millionate MT and 83.5 parts of Luplanate MI in a reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a cooling condenser, and a dropping funnel, and stir while heating to 70 ° C., and use a dropping funnel to stir the intermediate. The mixture was slowly added dropwise over time and further stirred at 4 o'clock to obtain a polyisocyanate "hardener B3". The NCO% measured according to JIS-K1603 was 13.2%.

"Hardener B4"
71.45 parts of xylylene diisocyanate, a mixture of 4,4'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate in a reaction vessel equipped with a stirrer, nitrogen gas introduction tube, snider tube, cooling condenser, and dropping funnel. ) 46.26 parts were added and stirred while heating at 70 ° C., 92.28 parts of "polypoly A4" was added dropwise using a dropping funnel over 2 hours, and the mixture was further stirred for 4 hours to obtain "hardener B4". Got The NCO% measured according to JIS-K1603 was 15.1%.

"Hardener B5"
Mitsui Chemicals "Takenate D-110N" (trimethylolpropane adduct of metaxylylene diisocyanate non-volatile component 75.0% NCO% 11.5%) and Mitsui Chemicals "Takenate 500" (metaxylylene diisocyanate non-volatile content> 99 %, NCO% 44.6%) were mixed at a ratio of 50/50 (mass ratio) to obtain "hardener B5". The non-volatile content of the curing agent B1 is 87.5%, and the NCO% is 28.05%.

"Hardener B6"
"PASLIM VM108CP" manufactured by DIC Corporation was designated as "curing agent B6".

(Adhesive adjustment)
The adjusted polyols A1 to A8 and the curing agents B1 to B6 were blended in the ratios shown in Table 1 to prepare the adhesives 1 to 15.

<How to adjust water-based liquid ink>
(Adjustment of resin for water-based ink)
In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 191 parts by mass of polyoxytetramethylene glycol (molecular weight 2000), 141 parts by mass of isophorone diisocyanate, and 26 parts by mass of 2,2-dimethylolpropionic acid. By reacting in a mixed solvent of 28 parts by mass, 1,4-cyclohexanedimethanol and 200 parts by mass of methyl ethyl ketone, an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular terminal was obtained.

Next, 20 parts by mass of a 50% potassium hydroxide aqueous solution was added to neutralize a part or all of the carboxyl groups of the urethane prepolymer, and 700 parts by mass of water and 9.0 parts by mass of an 80% hydrazine aqueous solution were added sufficiently. An aqueous dispersion of a urethane resin was obtained by stirring the mixture, and then aging and solvent removal were performed to obtain a resin for an aqueous liquid ink having a non-volatile content of 40% by mass.

(Adjustment of water-based liquid ink)
Using the obtained resin for water-based liquid ink, the mixture was stirred and mixed with the following composition, and then kneaded with a bead mill to prepare a kneaded meat base.
[Meat base combination]
FASTPGEN BLUE LA5380 Indigo pigment (manufactured by DIC) 15 parts Resin for water-based liquid ink 40 parts Nonionic pigment dispersant (manufactured by BYK) 10 parts Isopropyl alcohol 3 parts Water 8 parts Silicone defoamer (manufactured by BYK) 0. Part 2

After adding 10 parts of the resin for water-based liquid ink and 4 parts of water to the obtained kneaded meat base, the viscosity of the water-based liquid ink becomes 16 seconds (25 ° C.) with Zahn Cup # 4 (manufactured by Rigosha). Water was added in the same manner to obtain a water-based liquid ink. The amount of water used for adjusting the viscosity was 5 parts, the non-volatile content of the water-based liquid ink was 58%, and the surface tension at 25 ° C. was 35 mN / m. The surface tension was measured using an automatic surface tension meter DY-300 manufactured by Kyowa Interface Science Co., Ltd. based on the Whyhelmy method. The composition of the obtained water-based liquid ink is as follows.
[Mixing of water-based liquid ink]
FASTPGEN BLUE LA5380 Indigo pigment (manufactured by DIC) 15 parts Resin for water-based liquid ink 50 parts Nonionic pigment dispersant (manufactured by BYK) 10 parts Isopropyl alcohol 3 parts Water 17 parts Silicon-based defoamer (manufactured by BYK) 0. Part 2

<Manufacturing method of laminate for evaluation>
(Manufacture of OPP film 1 having an aluminum oxide layer)
An anchor coating agent mixed with a silane coupling agent, an acrylic polyol, and an isocyanate curing agent is applied to one surface of an OPP film having a thickness of 20 μm whose surface orientation coefficient Δ is adjusted to 0.011 by biaxial stretching treatment to obtain a thickness. After forming a 0.3 μm anchor coat layer, an aluminum oxide layer having a thickness of 15 nm was formed by an electron beam heating method. This film will also be referred to as OPP film 1 below.

(Manufacturing of OPP films 2 and 2'having an aluminum oxide layer)
On the aluminum oxide layer of the OPP film 1, a gas barrier coating agent adjusted according to the formulations shown in Tables 2 and 3 or a coating agent adjusted according to the formulations shown in Table 4 is applied in a coating amount of 1.0 g / m ^{2 using a bar coater.} It was coated so that it became (solid content). Immediately after coating, the OPP film is heated in a dryer at 60 ° C. for 1 minute to have a gas barrier coating layer on the aluminum oxide layer (hereinafter also referred to as OPP film 2), and an OPP film having a coating layer on the aluminum oxide layer. (Hereinafter also referred to as OPP film 2') was obtained.

(Manufacturing of OPP film 3 having an aluminum oxide layer)
Water-based liquid ink is printed on OPP film 1 using a Flexoprof100 test printing machine (Testing Machines, Inc., Anilox 200 lines / inch) with a solid pattern of 240 mm in length and 80 mm in width, and then dried with a dryer to dry the OPP film. A printing layer was provided on the aluminum oxide layer of No. 3 to form an OPP film 3. The coating amount of the printing layer (solid content of the coated water-based liquid ink) was 1.0 g / m ² .

The OPP film 2 was used instead of the OPP film 1, and the OPP film 4 was obtained in the same manner as in the production of the OPP film 3 except that the printing layer was provided on the gas barrier coating layer. Further, OPP film 2'was used instead of OPP film 1, and OPP film 4'was obtained in the same manner as in the production of OPP film 3 except that a printing layer was provided on the coating layer.

(Manufacturing method of laminate for evaluation)
Using the OPP film obtained as described above, the evaluation laminates of Examples 1 to 19 and Comparative Examples 1 to 3 were produced by any of the following adhesive coating methods 1 or 2. The adhesives and adhesive coating methods used in the production of the laminate are shown in Tables 2 to 4.

<Adhesive coating method>
(Method 1)
Using a bar coater, apply the adjusted adhesive on the aluminum oxide layer of OPP film 1, the gas barrier coating layer of OPP film 2, and the OPP film so that the coating film ^{amount is 3.0 g / m 2 (solid content).} It was applied on the coating layer of 2'and on the printing layers of the OPP films 3, 4, and 4', respectively, and the diluting solvent was volatilized and dried by a dryer set at a temperature of 70 ° C. Next, the adhesive surface of the OPP film coated with the adhesive and the LLDPE film (TUX-HC manufactured by Mitsui Chemicals Tohcello Co., Ltd., thickness 40 μm) were bonded together. Aging was carried out at 40 ° C. for 2 days to obtain a laminate.

(Method 2)
The prepared adhesive is heated to about 70 ° C., and a solvent-free test coater is used on the aluminum oxide layer of the OPP film 1, the gas barrier coating layer of the OPP film 2, the coating layer of the OPP film 2', and the OPP. A coating amount of 2.5 g / m ² (solid content) was applied onto the print layers of the films 3, 4 and 4', respectively, and the adhesive surfaces of the OPP films 1 to 4 to which the adhesive was applied were applied. An LLDPE film (TUX-HC manufactured by Mitsui Kagaku Tohcello, thickness 40 μm) was bonded. Aging was carried out at 40 ° C. for 2 days to obtain a laminate.

<Evaluation>
(Evaluation of gas barrier property: Oxygen permeability)
The oxygen transmission rate (OTR) is measured according to JIS-K7126 (isopressure method) using the oxygen transmission rate measurement device OX-TRAN1 / 50 manufactured by Mocon Co., Ltd. in an atmosphere of temperature 23 ° C. and humidity 0% RH. , The temperature was 23 ° C. and the humidity was 90% RH. RH represents relative humidity. The unit of oxygen permeability is cc / day, atm, and m ² . The results are summarized in Tables 2-4.

(Evaluation of gas barrier property: Water vapor permeability)
The water vapor transmittance (MVTR) was measured according to JIS-K7129 in an atmosphere of a temperature of 40 ° C. and a humidity of 90% RH using a water vapor permeability measuring device 7001 manufactured by Irinoi. The unit of oxygen permeability is g / m ² · day. The results are summarized in Tables 2-4.

(Oxygen permeability after bending test)
The aging-finished laminate was adjusted to a size of 30 cm x 20 cm, and a bending test was conducted with a Gelboflex tester (BE-1006 Gelboflex tester with constant temperature bath, Tester Sangyo Co., Ltd.) according to ASTM F392. .. The bending test was carried out at 440 ° / 90 mm, linear motion 65 mm, and 23 ° C. under the conditions of 5 times of bending, and the oxygen permeability after the gelboflex treatment was measured. The unit is cc / m ² , day, atm. The results are summarized in Tables 2-4.

(Water vapor permeability after bending test)
The aging-finished laminate was adjusted to a size of 30 cm x 20 cm, and a bending test was conducted with a Gelboflex tester (BE-1006 Gelboflex tester with constant temperature bath, Tester Sangyo Co., Ltd.) according to ASTM F392. .. The bending test was carried out at 440 ° / 90 mm, linear motion 65 mm, and 23 ° C. under the conditions of 5 times of bending, and the water vapor transmittance after the gelboflex treatment was measured. The unit is g / m ² · day. The results are summarized in Tables 2-4.

(Measuring method of laminate strength)
The evaluation laminate of OPP film 2 or OPP film 2'and LLDPE film is cut to a width of 15 mm parallel to the coating direction, and the biaxially stretched OPP film and LLDPE film are sandwiched between A & Co., Ltd. Using "Tencilon universal testing machine STB-01" manufactured by D., the ambient temperature was set to 25 ° C., the peeling speed was set to 300 mm / min, and the tensile strength when peeled by the 180 degree peeling method was defined as the lamination strength. The unit of adhesive strength was N / 15 mm. Further, "OPP cut" in the table means that the material of the adherend (OPP film in this case) is destroyed due to the strong adhesive strength, that is, the adhesive strength itself is good.

As is clear from Examples and Comparative Examples, the laminated body of the present invention has low oxygen and water vapor transmittances, is excellent in barrier properties, and maintains its characteristics even after a bending test. On the other hand, it can be seen that the laminates of Comparative Examples 1 to 3 are inferior in gas barrier property and the performance is significantly deteriorated after the bending test.

The laminate of the present invention exhibits excellent gas barrier properties as compared with conventional gas barrier laminates due to its composition. From this, the laminate of the present invention can be suitably used as a packaging material, particularly as a packaging material that requires barrier properties such as food, daily necessities, electronic materials, and medical use.

Claims

A substrate made of biaxially stretched polypropylene and
The aluminum oxide layer arranged on the base material and
The gas barrier coating agent layer arranged on the aluminum oxide layer and
A laminate having a gas barrier adhesive layer arranged on the gas barrier coating agent layer.
The gas barrier coating agent is a coating agent containing a resin (A) having a carboxyl group, a divalent metal compound (B), and an alcohol (C), and the content of the alcohol (C) in the composition is high. The laminate according to claim 1, wherein the content is 85 to 98 wt% and the water content in the composition is 1% or less.
The resin (A) having a carboxyl group is at least one selected from homopolymers or copolymers of monomers selected from acrylic acid, methacrylic acid, maleic acid and itaconic acid, and aspartic acid. Item 2. The laminate according to any one of Items 1 and 2.
The laminate according to any one of claims 1 to 3, wherein the divalent metal compound (B) is at least one selected from a zinc compound, a magnesium compound, and a calcium compound.
The laminate according to any one of claims 1 to 4, wherein the alcohol (C) is at least one selected from methanol, ethanol, propanol, and butanol.
A packaging material made of the laminate according to any one of claims 1 to 5.