TW202114861A - Gas barrier laminate and packaging material - Google Patents

Abstract

The present invention provides: a laminate which is capable of, even if an OPP film comprising an aluminum oxide layer is used when manufacturing a gas barrier laminate by bonding a plurality of films using an adhesive, exhibiting gas barrier properties comparable to those of a PET film comprising an aluminum oxide layer; and a packaging material using said laminate. This laminate is characterized by having a base material composed of biaxially drawn polypropylene, an aluminum oxide layer disposed on the base material, and a gas barrier adhesive layer disposed on the aluminum oxide layer. This packaging material is obtained by using said laminate.

Description

Gas barrier laminates, packaging materials

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

Packaging materials such as food and beverages not only need to be able to protect the strength of the contents from various distribution, refrigeration, storage, or heat sterilization, etc., to protect the strength of the contents, or properties that are not easy to break, retort resistance, heat resistance, etc., but also Various functions such as excellent transparency of the contents can be confirmed. On the other hand, when the bag is sealed by heat sealing, a non-stretched polyolefin-based film with excellent heat workability is required, but the non-stretched polyolefin film still has many functions that are insufficient as a packaging material.

Therefore, the aforementioned packaging materials are widely used in composite flexible films formed by combining different types of polymer materials. Generally speaking, the composite flexible film system includes: a thermoplastic plastic film layer that serves as an outer layer for protecting products or various functions, and a thermoplastic plastic film layer that serves as a sealing layer. In the case where the barrier function to maintain the food state and the visibility of the contents are required, some people propose to use, for example, polyethylene terephthalate film (PET film) or stretched polypropylene film (OPP film) A film formed by vapor-depositing aluminum oxide thereon is used as a plastic film (Patent Document 1). [Prior Technical Literature] [Patent Literature]

Patent Document 1 　 JP 2001-260266 A

[The problem to be solved by the invention]

OPP film has low adhesion to alumina, and compared to PET film with alumina layer, OPP film with alumina layer has poor gas barrier properties. Furthermore, if it is heated by boiling/retorting treatment, etc. Sterilization treatment may cause delamination (delamination). In order to improve the adhesion between the OPP film and alumina, studies have been conducted to adjust the orientation of the OPP film before the vapor deposition of alumina, and to perform surface treatments such as plasma treatment on the OPP film. However, no matter what In either method, it is difficult to achieve the same gas barrier properties as the PET film with the alumina layer on the OPP film with the alumina layer.

The present invention was completed in view of such circumstances, and its object is to provide a laminate that can exhibit the same gas barrier properties as the PET film with an alumina layer even when an OPP film with an alumina layer is used. ,Packaging Materials. [Means to solve the problem]

The present invention relates to a laminate and a packaging material obtained by using the laminate. The laminate system has: a base material comprising biaxially stretched polypropylene, an alumina layer arranged on the base material, and an oxide layer arranged on the base material. The gas barrier adhesive layer on the aluminum layer. [Effects of Invention]

According to the laminate of the present invention, the OPP film with an aluminum oxide layer can exhibit the same degree of gas barrier properties as the PET film with an aluminum oxide layer, and the OPP film with an aluminum oxide layer can be used to provide gas barrier Excellent packaging materials.

[Form to implement the invention]

＜Laminated body＞ The laminated system of the present invention has a base material containing biaxially stretched polypropylene, an alumina layer disposed on the base material, and a gas barrier adhesive layer disposed on the alumina layer. In addition to these layers, it may also have a sealant layer, a printing layer, an anchor coat, an over coat, and the like. The constitution of the present invention will be described in detail below.

(Substrate) The base material used in the laminate of the present invention contains biaxially stretched polypropylene. As a raw material, a propylene-based resin containing a single polymer of propylene, a copolymer of propylene and other monomers, and a mixture of a single polymer of propylene and a copolymer can be mentioned. It is also possible to use a single-layer or two-layer co-extrusion method to form a film or sheet containing these raw materials (in addition, if there is no special description below, the film is also the collective name of film and sheet), and the film is formed in a double layer. It extends in the axial direction.

As a method of extending in two directions, a conventionally known method can be used, for example, the raw material is melted by an extruder, and the material is extruded by a ring die or a T-shaped die, followed by rapid cooling, thereby manufacturing substantially Unshaped and unoriented unstretched film. After that, the unstretched film is stretched in the direction of the film's travel (longitudinal axis) and in the direction of the film's travel (longitudinal axis) by methods such as tentering sequential biaxial stretching, tentering simultaneous biaxial stretching, and tubular simultaneous biaxial stretching. The direction of travel is the direction extending at right angles (horizontal axis), thereby making it possible to manufacture. The stretching ratio can be appropriately selected according to the polypropylene raw material, but it is generally preferably 2 to 10 times in the longitudinal direction and the lateral direction, respectively.

The film thickness of the substrate is not particularly limited, and from the viewpoint of moldability and transparency, it may be appropriately selected within the range of 1 to 300 μm. Preferably it is 1-100 micrometers, More preferably, it is the range of 20-50 micrometers. If it is less than 1 μm, the strength will be insufficient, and if it exceeds 300 μm, the rigidity will become too high and processing may become difficult.

The substrate used in the present invention preferably has a plane orientation coefficient Δ obtained by a phase difference measurement method in the range of 0.005 to 0.020. Thereby, the adhesion between the alumina layer and the base material described later can be improved to a level that can sufficiently withstand boiling and retorting treatments.

As a method of adjusting the planar orientation coefficient Δ of the substrate to the range of 0.005 to 0.020, for example, a heat fixing step is performed after biaxial stretching, and the conditions of biaxial stretching and heat fixing are appropriately selected to control Method of plane orientation coefficient Δ. For example, after biaxial stretching, heat fixing is performed at a low temperature for a long time, whereby the aforementioned plane orientation coefficient Δ can be adjusted to a desired range. In addition, the surface may be modified by surface treatment such as reactive ion etching (RIE) treatment, which will be described later, so that the plane orientation coefficient Δ is in the range of 0.005 to 0.020. Commercial products whose plane orientation coefficient Δ is adjusted to the range of 0.005 to 0.020 in advance can also be used, or the surface of the substrate can be modified immediately before forming the alumina layer.

In addition, the substrate used in the present invention preferably has an orientation angle measured by a phase difference measurement method, which is 50° to 90° or -50° to -90° with respect to the direction of travel. As a result, the adhesion between the alumina layer and the base material described later can be improved to a level that can sufficiently withstand boiling and retorting treatments. Here, the orientation angle is defined as follows: taking the direction of travel as 0°, if the molecular chain is inclined to the left side, it is +, and if the molecular chain is inclined to the right side, it is -.

The orientation angle in the direction of travel can be obtained by the phase difference measurement method using visible light, the molecular orientation measurement method using microwaves, etc. However, in the case of the molecular orientation measurement method using microwave, the measurement value from the surveyor is not uniform. Big. In contrast, the phase difference measurement method does not vary from person to person, and can measure stably, has less unevenness of the person, and can accurately measure the orientation angle. Therefore, the phase difference measurement method should be adopted for the measurement of the orientation angle relative to the direction of travel.

Such a substrate can be obtained by biaxial stretching and thermal fixing. The orientation angle can be controlled by appropriately selecting the conditions of biaxial extension and thermal fixation. For example, after biaxial extension, the central part is cut out with respect to the direction of travel and used, whereby the orientation angle of the substrate can be selected within a desired range.

The base material can also contain additives according to the demand. Specifically, improvement, modification processability, heat resistance, weather resistance, mechanical properties, dimensional stability, oxidation resistance, smoothness, mold release, flame retardancy, mildew resistance, electrical properties, strength, etc. are taken as For the purpose, plastic admixtures or additives such as slip agents, crosslinking agents, antioxidants, ultraviolet absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, etc. can be added. The amount of additives added should be adjusted within a range that does not affect other properties.

(Surface treatment) In order to improve the adhesion of the alumina layer, any surface treatments can be applied to the substrate, such as corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen or nitrogen, and physical treatment such as glow discharge treatment. Or chemical treatments such as oxidation treatment using chemicals, or other treatments. In particular, the discharge treatment is preferable because the plane orientation coefficient Δ of the substrate can be adjusted within the expected range. The discharge treatment is not particularly limited, but RIE treatment is preferred.

The RIE treatment can be performed using, for example, a winding-type in-line device, and a flat-type processing device that applies a voltage to a cooling drum provided with a substrate can be used. The method of RIE processing the substrate with a flat processing device. The electrode (cathode) is arranged inside the processing drum (cooling drum), and the substrate is transported along the processing drum while the ions in the plasma are applied to the surface. Instead, RIE processing is performed. With this method, the substrate can be placed close to the cathode, and the RIE process can be performed by obtaining a high self-biased voltage.

Alternatively, the RIE treatment can also be performed using a hollow anode/plasma treatment device. The hollow anode/plasma processing device is equipped with a processing drum functioning as an anode, for example. The cathode and the shielding plates arranged at both ends of the cathode are arranged so as to face the treatment drum outside the treatment drum, and the cathode is formed in a box shape with an opening. The opening of the cathode is opened facing the processing drum, and the shielding plate has a curved shape along the processing drum. The gas introduction nozzle is arranged above the cathode, and introduces gas into the gap between the processing drum and the cathode and between the processing drum and the shielding plate. The matching box is arranged on the back of the cathode.

When the substrate is subjected to RIE processing with such a hollow anode/plasma processing device, a voltage is applied to the cathode from the matching box while conveying the substrate along the processing drum, between the processing drum into which the gas is introduced and the cathode and the shielding plate. Plasma is generated, and free radicals in the plasma are gathered to the treatment drum as the anode, thereby causing the free radicals to act on the surface of the substrate.

In the RIE process, it is preferable to assemble the magnet in the hollow anode electrode and use the magnetic assist/hollow anode. As a result, it is possible to perform a more powerful and stable plasma surface treatment at a high speed. The magnetic field generated from the magnetic electrode can further improve the plasma confinement effect, and obtain a high ion current density with a large self-sufficient bias voltage.

As the type of gas used for the pretreatment by RIE, for example, argon, oxygen, nitrogen, and hydrogen can be used. These gases may be used alone or in combination of two or more kinds. In RIE processing, two or more processing devices can also be used for continuous processing. At this time, the two or more processing devices used do not need to be the same. For example, it is also possible to process the substrate with a flat-type processing device, and then continuously use the hollow anode/plasma processing device for processing.

(Anchor Coating) In the laminate of the present invention, an anchor coating layer may be provided on the base material in advance before the alumina layer is formed. The anchor coating system can be formed by coating an anchor coating agent on a substrate and drying it. Thereby, the adhesion between the base material and the alumina layer can be improved, and the flatness of the alumina layer formation surface can be improved by the leveling effect of the anchor coating agent, and the formation of cracks and other film defects can be reduced And uniform aluminum oxide film.

唑啉基之樹脂、改質苯乙烯樹脂、改質矽樹脂或烷基鈦酸等者。此等可單獨或組合2種以上來使用。Examples of anchor coating agents include: solvent-soluble or water-soluble polyester resins, isocyanate resins, urethane resins, acrylic resins, vinyl alcohol resins, ethylene vinyl alcohol resins, vinyl modified resins, Epoxy resin, containing

Oxazoline-based resin, modified styrene resin, modified silicon resin, alkyl titanic acid, etc. These can be used alone or in combination of two or more kinds.

The thickness of the anchor coating is not particularly limited, but is preferably about 5 nm to 5 μm, more preferably 10 nm to 1 μm. Thereby, a uniform layer with suppressed internal stress can be formed on the substrate.

When an anchor coating is provided, in order to improve the coatability and adhesiveness of the anchor coating agent, it is also preferable to perform a discharge treatment on the surface of the substrate before the formation of the anchor coating.

(Alumina layer) The alumina layer is a layer containing alumina as a main component. Here, the main component means that more than 50% by mass of the components constituting the alumina layer is alumina. Preferably, 70% by mass or more of the components constituting the alumina layer is alumina, more preferably 90% by mass or more, and ideally 100% by mass. Alumina contains at least one of various aluminum oxides such as AlO, Al ₂ O, and Al ₂ O _3, and the content of each aluminum oxide can be adjusted according to the production conditions of the thin film layer.

The aluminum oxide layer preferably has a ratio of oxygen to aluminum (O/Al ratio) calculated by the XPS measurement method of 1.0 to 1.5. By this, it is transparent and exhibits high adhesion to the base material. If the O/Al ratio is too small, sufficient barrier properties cannot be ensured, and there is a concern that film defects such as coloring, impairing transparency, and cracks, are likely to occur.

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

The thickness of the aluminum oxide layer is preferably 5 nm to 300 nm, more preferably 10 nm to 300 nm. If the film thickness is too thin, a uniform layer cannot be formed, and there is a concern that sufficient barrier properties cannot be ensured. On the other hand, if the film thickness of the aluminum oxide layer is too thick, there is a concern that cracks will occur in the aluminum oxide layer due to stress.

The surface roughness of the aluminum oxide layer is preferably 3.5 μm or less, more preferably 2.5 μm or less, and still more preferably 2.0 μm or less. The lower limit of the surface roughness Rm is not particularly limited, but as an example, it is 1.0 μm or more. In addition, the surface roughness of the aluminum oxide layer here refers to the surface roughness of the surface of the aluminum oxide layer on the opposite side of the substrate, which is measured by the AFM measured with an atomic force microscope (hereinafter referred to as "AFM") The roughness Rms (root mean square roughness) value obtained by roughness analysis of the uneven image.

The surface roughness of the aluminum oxide layer will be affected by the surface roughness of the substrate, the presence or absence of the anchor coating, the particle size of the particles forming the aluminum oxide layer, and the film thickness of the aluminum oxide layer. If the surface roughness of the layer is within the above range, the gas barrier properties of the laminate can be improved.

In addition, the average particle diameter of the particles forming the alumina layer is preferably 20 nm or less. Thereby, the alumina layer can be filled with high density, and the irregularities on the surface of the base material can be efficiently covered without gaps, and a laminate having excellent gas barrier properties can be obtained. In addition, the average particle diameter of the particles forming the alumina layer is more preferably 15 nm or less, and still more preferably 10 nm or less. The lower limit is not particularly limited. The average particle size of the particles forming the aluminum oxide layer is the same as the measurement of the surface roughness of the aluminum oxide layer, and can be obtained by analyzing the AFM uneven image.

The aluminum oxide layer can be formed by a vacuum evaporation method, a sputtering method, an ion implantation method, a chemical vapor growth method (CVD), or the like. In consideration of productivity, a vacuum evaporation method is preferred. When the aluminum oxide layer is formed by a vacuum vapor deposition method, a means of generating high-density plasma can also be used in combination. As the heating method of the vapor deposition material, an electron beam (EB) method, a high-frequency induction heating method, a resistance heating method, etc. can be used. A high-energy high-density plasma can be used to collide with vapor-deposited particles vaporized or sublimated by a vacuum vapor deposition method to improve the film quality of the aluminum oxide layer such as denseness and improve barrier properties. As a means for generating high-density plasma, inductively coupled (ICP) plasma, spiral wave plasma, microwave plasma, hollow cathode discharge, and the like can be cited.

唑啉基之樹脂、改質苯乙烯樹脂、改質矽樹脂及烷基鈦酸等之中的樹脂者。保護塗層係可藉由使用此等材料的單獨層、或2種以上的積層所構成。(Protective coating) The laminate of the present invention can also form a protective coating on the alumina layer, which can improve the protection of the alumina layer and the adhesion with the gas barrier adhesive layer and the optionally formed printed layer. The protective coating can be formed by applying a protective coating agent on the alumina layer and drying it. Examples of protective coating agents include polyester resins, isocyanate resins, urethane resins, acrylic resins, vinyl alcohol resins, and ethylene/vinyl alcohol copolymers (EVOH) selected from solvent-soluble or water-soluble polyester resins, isocyanate resins, urethane resins, and acrylic resins. Resin, vinyl modified resin, epoxy resin, containing

Oxazoline-based resins, modified styrene resins, modified silicon resins, and alkyl titanic acid resins. The protective coating can be composed of a single layer of these materials or a stack of two or more types.

The protective coating is also preferably: in a solution obtained by dissolving a water-soluble polymer with water or a water/alcohol mixed solvent, a metal alkoxide is directly mixed or subjected to a treatment such as hydrolysis in advance, and the mixed solution It is coated on the alumina layer and dried to form.

Examples of water-soluble polymers include polyvinyl alcohol resins and ethylene/vinyl alcohol copolymers. Commercial products can also be used for water-soluble polymers. Examples of commercial products of polyvinyl alcohol-based resins include RS-110 (manufactured by Kuraray Co., Ltd., RS polymer, saponification degree: 99%, polymerization degree: 1,000) , Kuraray Poval LM-20SO (manufactured by Kuraray Co., Ltd., saponification degree: 40%, polymerization degree: 2,000), Gohsenol NM-14 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., saponification degree: 99%, polymerization degree: 1,400) Wait. Commercial products of ethylene/vinyl alcohol copolymers include EVAL EPF101 (manufactured by Kuraray Co., Ltd., ethylene content: 32 mol%), Soarnol D2908 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., ethylene content: 29 Mole%) etc.

Examples of metal alkoxides include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane, and γ-glycidoxypropyltrimethoxy Silane coupling agents such as glycidyl silane, γ-glycidoxypropylmethyl diethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc., can be combined with one or two types Use the above.

The protective paint may also contain fillers. It can improve the gas barrier, abrasion, and smoothness of the protective coating. As the filler, for example, silica sol, alumina sol, particulate inorganic filler, layered inorganic filler, etc. can be used alone or in combination of two or more kinds. The protective coating agent may also include coupling agents such as a silane coupling agent. When the protective coating is formed by polycondensation, the protective coating may also include a catalyst.

The thickness of the protective coating is preferably 0.01 to 100 μm, more preferably 0.1 to 50 μm. If it is less than 0.01 μm, the improvement of gas barrier properties is insufficient, and if it is more than 100 μm, cracks tend to occur.

(Gas Barrier Adhesive Layer) The gas barrier adhesive layer is a cured coating film of a gas barrier adhesive, and is arranged on the alumina layer directly or through other layers such as a protective coating. The gas barrier adhesive that can be used is not particularly limited as long as it has gas barrier properties. In addition, in this specification, the gas barrier adhesive refers to those that satisfy at least one of the following conditions: ^{the cured coating film of the adhesive coated with 3g/m 2} (solid content) has an oxygen barrier of 300cc/m ² /day/atm or less; or water vapor barrier below 120g/m ² /day. As a commercially available product, the "PASLIM" series such as PASLIM VM001 or PASLIM J350X manufactured by DIC Co., Ltd., and "MAXIVE" manufactured by Mitsubishi Gas Chemical Co., Ltd. can be cited.

As the adhesive with gas barrier properties used in the present invention, a two-component adhesive composed of a polyol composition (A) and a polyisocyanate composition (B) can be preferably cited, wherein the polyol composition The substance (A) contains at least one polyester polyol of the following (A1) to (A5), and the polyisocyanate composition (B) contains a compound having at least two isocyanate groups in one molecule (hereinafter sometimes only Known as isocyanate compounds).

(1) Polyester polyol (A1) obtained by reacting carboxylic anhydride or polycarboxylic acid with a polyester polyol having 3 or more hydroxyl groups (2) Polyester polyol with polymerizable carbon-carbon double bond (A2) (3) Polyester polyol with glycerol skeleton (A3) (4) Polyester polyol obtained by polycondensation of ortho-oriented polycarboxylic acid and polyol (A4) (5) Polyester polyol with isocyanuric acid ring (A5)

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

The polycarboxylic acid used in the preparation of the polyester polyol (A1) preferably contains at least one of phthalic acid and phthalic anhydride. Polyester polyols obtained by using these compounds as polycarboxylic acids have excellent gas barrier properties and adhesiveness. By using phthalic acid and phthalic anhydride, the adhesive has excellent gas barrier properties. It is presumed that the reason is that the rotation of the polyester chain obtained by using phthalic acid or its anhydride is suppressed. The reason for the excellent adhesiveness is presumably because the polyester chain is asymmetrical, which results in non-crystalline properties and sufficient substrate adhesion.

Examples of polyhydric carboxylic acids having three or more valences include trimellitic acid and its acid anhydrides, pyromellitic acid and its acid anhydrides, and the like. In order to prevent gelation during synthesis, it is preferable to use a trivalent carboxylic acid as a trivalent or higher polycarboxylic acid.

In the range that does not impair the effects of the present invention, other polycarboxylic acids may be copolymerized. Specifically, examples include: aliphatic polycarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, and dodecane dicarboxylic acid; maleic anhydride, maleic acid, fumaric acid, etc. containing unsaturated bonds The polycarboxylic acid; 1,3-cyclopentane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid and other alicyclic polycarboxylic acids; terephthalic acid, isophthalic acid, pyromellitic acid, trimellitic acid Acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalenedicarboxylic 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 ester-forming derivatives of these dihydroxycarboxylic acids, etc. Aromatic polyvalent carboxylic acid etc. can use 1 type or 2 or more types together. Among them, succinic acid, 1,3-cyclopentane dicarboxylic acid, isophthalic acid and anhydrides thereof are more preferred.

The polyol used in the preparation of the polyester polyol (A1) preferably contains at least 1 selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol and cyclohexane dimethanol. Kind. It is inferred that the smaller the number of carbon atoms between oxygen atoms, the less the molecular chain will become too soft, and oxygen will not penetrate easily, so it is particularly preferable to use ethylene glycol.

Examples of trivalent or higher polyols include glycerol, trimethylolpropane, trimethylolethane, ginseng (2-hydroxyethyl) isocyanurate, 1,2,4-butane Triol, neopentyl erythritol, dineopentaerythritol, etc. In order to prevent gelation at the time of synthesis, it is preferable to use a trihydric alcohol as a polyhydric alcohol with three or more valences.

In a range that does not impair the effects of the present invention, other polycarboxylic acids may be copolymerized. Specifically, examples include: 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol, dimethylbutanediol, butane Aliphatic diols such as ethyl propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol; hydroquinone, resorcinol, catechol, naphthalene glycol, biphenyl Phenol (biphenol), bisphenol A, bisphenol F, tetramethyl biphenol and these ethylene oxide extension products, hydrogenated alicyclic and other aromatic polyphenols, etc.

The polyester polyol (A1) can be obtained by reacting a polycarboxylic acid or its anhydride with a polyester polyol (a1) having 3 or more hydroxyl groups, which is a reaction product of the above-mentioned polycarboxylic acid and polyol obtain. The ratio of the hydroxyl groups that react with the polycarboxylic acid is preferably 1/3 or less of the hydroxyl groups of the polyester polyol (a1). The polycarboxylic acid or its anhydride to be reacted with the polyester polyol (a1) is preferably divalent or trivalent. Examples include: succinic anhydride, maleic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, benzene Dicarboxylic anhydride, 2,3-naphthalenedicarboxylic anhydride, trimellitic anhydride, etc., but not limited thereto.

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 polycarboxylic acid or a polyol.

Examples of polycarboxylic acids having polymerizable carbon-carbon double bonds include maleic anhydride, maleic acid, fumaric acid, 4-cyclohexene-1,2-dicarboxylic acid and its anhydrides, and 3-methyl- 4-cyclohexene-1,2-dicarboxylic acid and its anhydride, etc. Among them, it is inferred that the smaller the number of carbon atoms, the less the molecular chain becomes too soft, and the oxygen is not easily penetrated. Therefore, maleic anhydride, maleic acid, and fumaric acid are preferred.

In the range that does not impair the effects of the present invention, other polycarboxylic acids may be copolymerized. Specifically, examples include: aliphatic polycarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, and dodecane dicarboxylic acid; 1,3-cyclopentane dicarboxylic acid, 1,4-cyclohexane Alicyclic polycarboxylic acids such as alkane dicarboxylic acid; phthalic acid, terephthalic acid, isophthalic acid, pyromellitic acid, trimellitic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalene Dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid and the anhydrides of these dicarboxylic acids or Aromatic polycarboxylic acids such as ester-forming derivatives, p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid, and ester-forming derivatives of these dihydroxycarboxylic acids, etc., can be used singly or in combination of two More than species. Moreover, these acid anhydrides can also be used. Among them, in order to obtain gas barrier properties, succinic acid, 1,3-cyclopentane dicarboxylic acid, phthalic acid, anhydrides of phthalic acid, and isophthalic acid are more preferred, and phthalic acid is more preferred. And its anhydrides.

Examples of polyols having polymerizable carbon-carbon double bonds include 2-butene-1,4-diol.

It is also possible to copolymerize other polyols within a range that does not impair the effects of the present invention. Specifically, examples include ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, cyclohexane dimethanol, 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 two Alcohol; Hydroquinone, resorcinol, catechol, naphthalene glycol, biphenol, bisphenol A, bisphenol F, tetramethyl biphenol and these ethylene oxide extension products, hydrogenated aliphatic ring Aromatic polyphenols, etc. Among them, it is inferred that the smaller the number of carbon atoms between oxygen atoms, the less the molecular chain will become too soft, and the oxygen will not penetrate easily. Therefore, ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol and Cyclohexane dimethanol, more preferably, is ethylene glycol.

In addition, the polyester polyol (A2) with polymerizable carbon-carbon double bonds may also be formed by the reaction of polyester polyol (a2) with hydroxyl groups and carboxylic acid with polymerizable double bonds, or with carboxylic anhydride Things. Examples of carboxylic acids having polymerizable double bonds or anhydrides thereof include carboxylic acids having polymerizable double bonds such as maleic acid, maleic anhydride, or fumaric acid, unsaturated fatty acids such as octadecenoic acid and sorbic acid, etc. . The polyester polyol (a2) preferably has 3 or more hydroxyl groups. When the polyester polyol (a2) has two or less hydroxyl groups, the number of hydroxyl groups in the polyester polyol (A2) is 0 to 1, which is not likely to occur when reacting with the polyisocyanate composition (B) described later Molecule stretches, and there is a concern that adhesive strength will 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 crosslinking points between polymerizable double bonds will decrease, and it will be difficult to obtain gas barrier properties. If it exceeds 60% by mass, the number of cross-linking points will increase, and the flexibility of the cured coating film will decrease, making it difficult to obtain adhesive strength. In addition, in this specification, the ratio of the double bond component in the polyester polyol (A2) is calculated using the following formula (a). In the following formula, the single system refers to the polycarboxylic acid and polyol used in the synthesis of the polyester polyol (A2).

Furthermore, as polyester polyol (A2), drying oil or semi-drying oil can be mentioned. Examples of the drying oil or semi-drying oil include conventionally used drying oils and semi-drying oils having carbon-carbon double bonds.

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

(通式(1)中，R₁ ～R₃ 分別獨立為氫原子或下述通式(2)；但R₁ ～R₃ 之中至少一者表示下述通式(2)表示的基)。

(In the general formula (1), R ₁ to R ₃ are each independently a hydrogen atom or the following general formula (2); but _{at least one of R 1} to R ₃ represents a group represented by the following general formula (2)) .

(通式(2)中，n表示1～5的整數，X表示選自包含亦可具有取代基的1,2-伸苯基、1,2-伸萘基、2,3-伸萘基、2,3-蒽醌二基、及2,3-蒽二基之群組中的伸芳基，Y表示碳原子數2～6的伸烷基)。

(In the general formula (2), n represents an integer from 1 to 5, and X represents a group selected from 1,2-phenylene, 1,2-naphthylene, and 2,3-naphthylene which may have substituents. , 2,3-anthraquinone diyl group, and 2,3-anthraquinone diyl group in the aryl group, Y represents a C 2-6 alkylene group).

The polyester polyol (A3) may also be _{a compound in which any one of R 1} , R ₂ and R ₃ is a group represented by the general formula (2), and is compatible with any two of _{R 1} , R ₂ and R ₃ The compound of the group represented by the formula (2) and any two or more compounds among the compounds in which all of _{R 1} , R ₂ and R _{3 are the groups represented by the general formula (2) become a mixture.} More preferably, all of R ₁ to R ₃ are groups represented by the general formula (2).

In the general formula (2), when X is substituted by a substituent, it may be substituted by one or more substituents, and the substituent is bonded to any carbon atom different from the free radical on X. Examples of the substituent include a chloro group, a bromo group, a methyl group, an ethyl group, an isopropyl group, a hydroxyl group, a methoxy group, an ethoxy group, a phenoxy group, a methylthio group, a phenylthio group, and a cyano group. , Nitro, amino, phthalimide, carboxyl, carboxamide, N-ethyl carboxamide, phenyl or naphthyl, etc.

As specific examples of Y in the general formula (2), ethylene, propylene, butylene, neopentylene, 1,5-pentylene, 3-methyl-1,5-pentylene C2-6 alkylene groups such as hexylene, 1,6-hexylene, methylpentylene, and dimethylbutylene. Preferably they are propylene and ethylene, and more preferably are ethylene.

Polyester polyol (A3) is obtained by reacting glycerol, aromatic polycarboxylic acid whose carboxylic acid is substituted to the ortho position or its anhydride, and polyhydric alcohol as essential components.

Examples of the aromatic polycarboxylic acid or its anhydride in which the carboxylic acid is substituted to the ortho position include phthalic acid or its anhydride, naphthalene 2,3-dicarboxylic acid or its anhydride, naphthalene 1,2-dicarboxylic acid or its anhydride , Anthraquinone 2,3-dicarboxylic acid or its anhydride, and 2,3-anthracene dicarboxylic acid or its anhydride, etc. These compounds may also 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 isopropyl group, a hydroxyl group, a methoxy group, an ethoxy group, a phenoxy group, a methylthio group, a phenylthio group, and a cyano group. , Nitro, amino, phthalimide, carboxyl, carboxamide, N-ethyl carboxamide, phenyl or naphthyl, etc.

As the polyvalent carboxylic acid, other polyvalent carboxylic acids may be copolymerized within a range that does not impair the effects of the present invention. Specifically, examples include: aliphatic polycarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, and dodecane dicarboxylic acid; maleic anhydride, maleic acid, fumaric acid, etc. containing unsaturated bonds The polycarboxylic acid; 1,3-cyclopentane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid and other alicyclic polycarboxylic acids; terephthalic acid, isophthalic acid, pyromellitic acid, trimellitic acid Acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, diphenic acid and its anhydrides, 1, 2-bis(phenoxy)ethane-p,p'-dicarboxylic acid and the anhydride or ester-forming derivatives of these dicarboxylic acids, p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid and the like Aromatic polyvalent carboxylic acids, such as ester-forming derivatives of dihydroxycarboxylic acids, etc., can be used singly or in combination of two or more. Among them, succinic acid, 1,3-cyclopentanedicarboxylic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, and diphthalic acid are preferred.

As the polyol, an alkanediol having 2 to 6 carbon atoms can be exemplified. For example, ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol Diols such as alcohol and dimethyl butanediol.

Moreover, in the range which does not impair the effect of this invention, a polyhydric alcohol other than glycerol and a C2-C6 alkanediol may be copolymerized. Specifically, exemplified: erythritol, neopentylerythritol, dineopentylerythritol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetraethylene glycol, triethylene glycol Aliphatic polyols such as propylene glycol, alicyclic polyols such as cyclohexane dimethanol, tricyclodecane dimethanol, hydroquinone, resorcinol, catechol, naphthalene glycol, biphenol, bisphenol A , Aromatic polyphenols such as bisphenol F, tetramethylbiphenol, and these ethylene oxide elongations, and hydrogenated alicyclics.

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

In addition, P in the above formula (b) refers to polyester polyol (A3). The mass of the resin solid content of the gas barrier adhesive is based on the total mass of the polyol composition (A) and polyisocyanate composition (B) used, deducting the diluting solvent (in the case of dry lamination adhesive), polyol The mass obtained from the mass of the volatile component and the inorganic component contained in the isocyanate composition (B).

Polyester polyol (A4) obtained by polycondensation of ortho-oriented polycarboxylic acid and polyol is composed of polycarboxylic acid containing at least one of phthalic acid and its anhydride, and It is composed of at least one polyol selected from the group of alcohol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol. Particularly preferred is a polyester polyol having a usage rate of 70 to 100% by mass of the aforementioned phthalic acid and its anhydride with respect to the total amount of polycarboxylic acid.

The polyvalent carboxylic acid requires any of phthalic acid and its anhydride, but other polyvalent carboxylic acids may be copolymerized within a range that does not impair the effects of the present invention. Specifically, the following can be used alone or in a mixture of two or more: as aliphatic polycarboxylic acids, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecane dicarboxylic acid, etc.; Maleic anhydride, maleic acid, fumaric acid, etc. of saturated bond polycarboxylic acids; 1,3-cyclopentane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, etc., as alicyclic polycarboxylic acids; Terephthalic acid, isophthalic acid, furandicarboxylic acid, pyromellitic acid, trimellitic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6- Naphthalenedicarboxylic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid and anhydride or ester-forming derivatives of these dicarboxylic acids; Polybasic acids such as hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid, and ester-forming derivatives of these dihydroxycarboxylic acids. Among them, succinic acid, 1,3-cyclopentane dicarboxylic acid, and isophthalic acid are more preferred.

The polyol includes at least one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexane dimethanol, but within a range that does not impair the effects of the present invention, It is also possible to copolymerize other polyols. Specifically, examples include: 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol, dimethylbutanediol, butane Aliphatic diols such as ethyl propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol; hydroquinone, resorcinol, catechol, naphthalene glycol, Biphenol, bisphenol A, bisphenol F, tetramethyl biphenol and these ethylene oxide extension products, hydrogenated alicyclic and other aromatic polyphenols, etc.

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

(通式(3)中，R₁ ～R₃ 分別獨立表示-(CH₂ )_n1 -OH(其中_n1 表示2～4)，或表示下述通式(4)表示的基；其中R₁ 、R₂ 及R₃ 的至少1者為通式(4)表示的基)。

(In the general formula (3), R ₁ to R ₃ each independently represent -(CH ₂ ) _n1 -OH (where _n1 represents 2 to 4), or represent a group represented by the following general formula (4); wherein R ₁ , At least one of R ₂ and R ₃ is a group represented by the general formula (4)).

(通式(4)中，n2表示2～4的整數，n3表示1～5的整數，X表示選自包含1,2-伸苯基、1,2-伸萘基、2,3-伸萘基、2,3-蒽醌二基、及2,3-蒽二基之群組且亦可具有取代基的伸芳基，Y表示碳原子數2～6的伸烷基)。

(In the general formula (4), n2 represents an integer from 2 to 4, n3 represents an integer from 1 to 5, and X represents selected from the group consisting of 1,2-phenylene, 1,2-naphthylene, and 2,3-phenylene A naphthyl group, a 2,3-anthraquinone diyl group, and a 2,3-anthraquinone diyl group and an arylene group that may have a substituent, and Y represents an alkylene group having 2 to 6 carbon atoms).

The polyester polyol (A5) may also be _{a compound in which any one of R 1} , R ₂ and R ₃ is a group represented by the general formula (4), and is compatible with any two of _{R 1} , R ₂ and R ₃ The compound of the group represented by the formula (4) and any two or more compounds among the compounds in which all of _{R 1} , R ₂ and R _{3 are the groups represented by the general formula (4) become a mixture.} More preferably, 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 -(CH 2} ) _n1 -may be linear or branched. Among them, n1 is preferably 2 or 3, most preferably 2.

In the general formula (4), when X is substituted by a substituent, it may be substituted by one or more substituents, and the substituent is bonded to any carbon atom of X that is different from the free radical. Examples of the substituent include a chloro group, a bromo group, a methyl group, an ethyl group, an isopropyl group, a hydroxyl group, a methoxy group, an ethoxy group, a phenoxy group, a methylthio group, a phenylthio group, and a cyano group. , Nitro, amino, phthalimide, carboxyl, carboxamide, N-ethyl carboxamide, phenyl or naphthyl, etc.

The substituent of X is preferably a hydroxyl group, a cyano group, a nitro group, an amino group, a phthalimino group, a carbamethanyl group, an N-ethylamino carbamate group, a phenyl group, and more preferably a hydroxyl group, a phenoxy group , Cyano, nitro, phthalimide, phenyl.

Specific examples of Y in the general formula (4) include: ethylene, propylene, butylene, neopentylene, 1,5-pentylene, 3-methyl-1 ,5-Pentylene, 1,6-hexylene, methylpentylene, dimethylbutylene and other C2-6 alkylene groups. Preferably they are propylene and ethylene, and more preferably are ethylene.

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

As the triol having an isocyanuric acid ring, for example, 1,3,5-gins (2-hydroxyethyl) isocyanuric acid, 1,3,5-gins (2-hydroxypropyl) ) Isocyanuric acid and other isocyanuric acid alkylene oxide adducts, etc.

Examples of the aromatic polycarboxylic acid or its anhydride in which the carboxylic acid is substituted to the ortho position include phthalic acid or its anhydride, naphthalene 2,3-dicarboxylic acid or its anhydride, naphthalene 1,2-dicarboxylic acid or its anhydride , Anthraquinone 2,3-dicarboxylic acid or its anhydride, and 2,3-anthracene dicarboxylic acid or its anhydride, etc. 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 isopropyl group, a hydroxyl group, a methoxy group, an ethoxy group, a phenoxy group, a methylthio group, a phenylthio group, and a cyano group. , Nitro, amino, phthalimide, carboxyl, carboxamide, N-ethyl carboxamide, phenyl or naphthyl, etc.

Examples of polyols include alkanediols having 2 to 6 carbon atoms, specifically ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, 1,5-pentanediol, and 3-methyl-1 ,5-pentanediol, 1,6-hexanediol, methylpentanediol, dimethylbutanediol and other diols.

Among them, polyester polyols (A5) with isocyanuric acid rings are preferred because they have excellent gas barrier properties and adhesion properties. They use 1,3,5-gins (2-hydroxyethyl) isotri Polycyanic acid or 1,3,5-ginseng (2-hydroxypropyl) isocyanuric acid is used as a triol compound with isocyanuric acid ring, and phthalic anhydride is used as a carboxylic acid to be substituted to ortho The aromatic polycarboxylic acid or its anhydride at the position, and ethylene glycol is used as the polyol.

The isocyanuric acid ring system is highly polar and does not form hydrogen bonds. Generally speaking, as a method to improve adhesion, a method of blending functional groups with high polarity such as hydroxyl, urethane bond, urea bond, amide bond, etc. has been known, but resins with these bonds It is easy to form intermolecular hydrogen bonds, which sometimes impairs the solubility of ethyl acetate, 2-butanone and other solvents commonly used in solvent-based adhesives, but polyester resins with isocyanuric rings will not impair the solubility This solubility allows easy dilution.

In addition, the isocyanuric acid ring is trifunctional. Therefore, a polyester polyol compound with an isocyanuric acid ring as the center of the resin skeleton and a polyester skeleton with a specific structure in its branch chain can obtain high-density resins. Link density. The inference is that by increasing the crosslinking density, the gaps through which gases such as oxygen pass can be reduced. The inference is that because of this, the isocyanuric acid ring does not form intermolecular hydrogen bonds but is highly polar and can obtain a high crosslink density, so that gas barrier properties and adhesiveness can be ensured.

From such a point of view, when the polyol composition (A) has polyester polyol (A5) as the main component, the solid content of the gas barrier adhesive contains the same three types of polyester polyol (A5). The content of the polycyanate ring is preferably 5% by mass or more. The isocyanuric acid ring refers to the residue after removing _{R 1} to R ₃ in the general formula (3) _{(C 3} N ₃ O ₃ =126.05), and is calculated using the following formula (b).

In addition, in the above formula (c), P means polyester polyol (A5). The mass of the resin solid content of the gas barrier adhesive is based on the total mass of the polyol composition (A) and polyisocyanate composition (B) used, deducting the diluting solvent (in the case of dry lamination adhesive), polyol The mass obtained from the mass of the volatile component and the inorganic component contained in the isocyanate composition (B).

The hydroxyl valence of the polyester polyol is preferably 20 mgKOH/g or more and 250 mgKOH/g or less. When the hydroxyl value is less than 20 mgKOH/g, because the molecular weight is too large, the viscosity of the polyol composition (A) becomes high, and good coating suitability cannot be obtained. When the hydroxyl value exceeds 250 mgKOH/g, the molecular weight is too small, and the crosslinking density of the cured coating film becomes too high, and 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. If the acid value is 20 mgKOH/g or more, good gas barrier properties and initial cohesion can be obtained through intermolecular interaction. The hydroxyl value of the polyester polyol can be measured by the hydroxyl value measurement method described in JIS-K0070, and the acid value can be measured by the acid value measurement method described in JIS-K0070.

If the number average molecular weight of the above-mentioned polyester polyol is 300 to 5,000, a crosslinking density with an excellent balance between adhesiveness and gas barrier properties can be obtained, which is particularly preferred. More preferably, the number average molecular weight is 350-3000. 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 concern that the film shifts during lamination or the laminated film floats. On the other hand, if the molecular weight is higher than 5000, the viscosity at the time of coating becomes too high, and there is a concern that the coating cannot be coated, or the adhesiveness is low and lamination cannot be performed. In addition, the number average molecular weight is calculated from the obtained hydroxyl valence 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 still more preferably 25°C or higher and 60°C or lower. If the glass transition temperature exceeds 80°C, the flexibility of the polyester polyol in the vicinity of room temperature is low, and therefore the adhesion to the substrate is poor, and there is a concern that the adhesiveness is lowered. On the other hand, if it is lower than -30°C, the molecular motion of the polyester polyol near normal temperature is intense, and therefore there is a concern that sufficient gas barrier properties cannot be obtained.

Polyester polyols can also be: polyester polyols (A1)～(A5) are stretched by urethane caused by the reaction with diisocyanate compounds to form a polyester polyamine with a number average molecular weight of 1,000 to 15,000 Base formate polyols. Polyester polyol stretched by urethane has excellent gas barrier properties and excellent initial cohesive force due to the presence of more than a certain molecular weight component and urethane bond, and can be excellent as a laminate Adhesive.

The polyisocyanate composition (B), which is a component of a two-component adhesive having gas barrier properties, contains an isocyanate compound. As the isocyanate compound, conventionally known compounds can be used without particular limitation, including: tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diisocyanate Phenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, or dimers and trimers of these isocyanate compounds, and those of these isocyanate compounds Excess amount, for example, ethylene glycol, propylene glycol, m-xylylene dimethyl alcohol, 1,3-bishydroxyethylbenzene, 1,4-bishydroxyethylbenzene, trimethylolpropane, glycerol, neopentyl alcohol Low molecular active hydrogen compounds such as tetraol, erythritol, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine, m-xylylenediamine and its alkylene oxide adducts, various polyesters Adducts obtained by reacting resins, polyether polyols, polyamide-based polymer active hydrogen compounds, etc. A polyester polyisocyanate obtained by reacting polyester polyols (A1) to (A5) and a diisocyanate compound with an isocyanate in the ratio of a hydroxyl group to an isocyanate group may be used. These can be used singly or in combination of two or more.

Moreover, as an isocyanate compound, a blocked isocyanate can also be used. Examples of the isocyanate blocking agent include phenols such as phenol, thiophenol, methylthiophenol, ethylthiophenol, cresol, xylenol, resorcinol, nitrophenol, and chlorophenol. Class, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime and other oximes, methanol, ethanol, propanol, butanol and other alcohols, chloroethanol, 1,3-dichloro-2-propanol and other halogen substitutions Alcohols, tertiary alcohols such as tertiary butanol, tertiary amyl alcohol, ε-caprolactam, δ-valerolactam, γ-butyrolactam, β-propiolactam and other internal amines , Others can also include: aromatic amines, imines, acetone, acetone acetate, ethyl malonate and other active methylene compounds, mercaptans, imines, ureas, two Aryl compounds, sodium bisulfite, etc. The blocked isocyanate can be obtained by the addition reaction of the above-mentioned isocyanate compound and the isocyanate blocking agent by a conventionally used appropriate method.

Among them, from the viewpoint of obtaining good gas barrier properties, it is more preferable to use xylylene diisocyanate, hydrogenated xylylene diisocyanate, toluene diisocyanate, or diphenylmethane diisocyanate. It is an isocyanate compound having a meta-xylene skeleton such as m-xylylene diisocyanate and hydrogenated m-xylylene diisocyanate.

Examples of the isocyanate compound having a meta-xylene skeleton include: a trimer of xylylene diisocyanate, a biuret compound synthesized by a reaction with an amine, and an additive formed by reacting with an alcohol. Adult. Since the solubility of the organic solvent used in the solvent-based adhesive is better than the trimer and the biuret, it is preferable to use an adduct when the adhesive is a solvent-based adhesive. As the adduct, it is possible to use adducts formed by reacting with alcohols appropriately selected from the above-mentioned low molecular active hydrogen compounds, but among them, trimethylolpropane, glycerol, triethanolamine, and methylene chloride are preferred. The adduct of toluene diamine and the adduct of ethylene oxide.

In addition, when a composition containing a polyester polyol with residual carboxylic acid groups such as polyester polyol (A1) is used as the polyol composition (A), the polyisocyanate composition (B) may also contain a ring Oxide. Examples of epoxides include: diglycidyl ether of bisphenol A and its oligomers, hydrogenated diglycidyl ether of bisphenol A and its oligomers, diglycidyl phthalate, and Diglycidyl phthalate, diglycidyl terephthalate, diglycidyl p-oxybenzoate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate Ester, diglycidyl succinate, diglycidyl adipate, diglycidyl sebacate, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanedi Alcohol diglycidyl ether, 1,6-hexanediol diglycidyl ether and polyalkylene glycol diglycidyl ether, triglycidyl trimellitate, triglycidyl isocyanurate Esters, 1,4-diglycidyloxybenzene, diglycidyl propylene urea, glycerol triglycidyl ether, trimethylol ethane triglycidyl ether, trimethylolpropane triglycidyl Propylene oxide, neopentyl erythritol tetraglycidyl ether, triglycidyl ether of glycerol alkylene oxide adduct, etc.

In the case of using epoxides, it can also be used for the purpose of accelerating hardening, and a commonly used epoxy hardening accelerator can be appropriately added within the scope of not impairing the purpose of the present invention.

When a composition containing a polyol having polymerizable carbon-carbon double bonds such as polyester polyol (A2) is used as the polyol composition (A), it can be used in combination to promote the polymerization of carbon-carbon double bonds As an example of conventional polymerization catalysts, transition metal complexes can be cited. The transition metal complex system is not particularly limited as long as it is a compound having the ability to oxidatively polymerize a polymerizable double bond. For example, metals such as cobalt, manganese, lead, calcium, cerium, zirconium, zinc, iron, copper and octanoic acid, naphthenic acid, neodecanoic acid, stearic acid, resin acid, tall oil fatty acid, tung oil fatty acid, flax can be used. Salt of seed oil fatty acid, soybean oil fatty acid, etc. The blending amount of the transition metal complex is preferably 0 to 10 parts by mass, and more preferably 0 to 3 parts by mass relative to the resin solid content contained in the polyol composition (A).

The polyol composition (A) and the polyisocyanate composition (B) are preferably based on the equivalent ratio of the hydroxyl group contained in the polyol composition (A) to the isocyanate group contained in the polyisocyanate composition (B) It is blended so as to become 1/0.5 to 1/10, and it is more preferable to blend so as to become 1/1 to 1/5. When the isocyanate compound is excessive, there is a concern that the excess isocyanate compound remaining in the cured coating film of the adhesive will bleed from the adhesive layer. On the other hand, if the reactive functional group contained in the polyisocyanate composition (B) is insufficient, the adhesive strength may be insufficient.

In the gas barrier adhesive, various additives may be blended within a range that does not impair the adhesion and gas barrier properties.

As such additives, inorganic fillers can also be used. Examples of inorganic fillers include silica, alumina, aluminum flakes, glass flakes, and the like. In particular, if a plate-shaped inorganic compound is used as an inorganic filler, the adhesive strength, gas barrier properties, light-shielding properties, etc. are improved, which is preferable. Examples of the plate-like inorganic compounds include hydrous silicates (layered silicate minerals, etc.), kaolinite-serpentine clay minerals (heileite, kaolinite, anderite, dickite, perlite, etc.) Chlorophyllite, chrysotile, etc.), pyrophyllite-talc (pyrophyllite, talc, wax serpentine, etc.), bentonite clay minerals (montmorillonite, belayite, nontronite, soap Stone, hectorite, sauconite, magnesite, etc.), clay minerals of the vermiculite group (vermiculite, etc.), mica or clay minerals of the mica group (mica such as muscovite, phlogopite, pearl mica, tetramethylsilane) (Tetrasilylic mica, band mica, etc.), chlorite group (spodite, chlorite, plagiochlorite, oolitic chlorite, nickel chlorite, etc.), hydrotalcite, plate-like sulfuric acid Barium, diaspore, aluminum polyphosphate, etc. These minerals can be natural clay minerals or synthetic clay minerals. The plate-shaped inorganic compound can be used singly or in combination of two or more kinds.

The plate-like inorganic compound may be an ionic one having a charge between layers, or a nonionic one having no charge. The presence or absence of interlayer charge does not directly affect the gas barrier properties of the adhesive layer. However, ionic plate-like inorganic compounds or inorganic compounds that are swellable to water have poor dispersibility for solvent-based adhesives. If the addition amount is increased, they may increase the viscosity of the adhesive and sometimes become Thixotropy, but there is a concern that the coating suitability will be reduced. Therefore, it is preferable that it does not have the nonionicity of the interlayer charge of the plate-like inorganic compound.

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 less than 0.1 μm, the detour path of oxygen molecules does not become long, and the improvement of gas barrier properties cannot be fully expected. 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 more preferably 20 μm or less. In addition, in this specification, the average particle size of the plate-like inorganic compound refers to the particle size that appears most frequently in the case of measuring the particle size distribution of the plate-like inorganic compound with a light scattering measuring device.

In order to improve the gas barrier property by the labyrinth effect of oxygen, it is preferable that the aspect ratio of the plate-shaped inorganic compound is high. 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 mass of the solid content of the polyol composition (A), the polyisocyanate composition (B), and the plate-shaped inorganic compound is taken as 100 mass, the plate-shaped inorganic compound The blending amount of the compound is 5-50 parts by mass.

The gas barrier adhesive may also include an adhesion promoter. Examples of the adhesion promoter include silane coupling agents such as hydrolyzable alkoxysilane compounds, titanate-based coupling agents, aluminum-based coupling agents, and epoxy resins. Silane coupling agents and titanate coupling agents are expected to improve the adhesion to various membrane materials.

When the gas barrier adhesive layer needs acid resistance, the gas barrier adhesive may also include a conventional acid anhydride. Examples of acid anhydrides include phthalic anhydride, succinic anhydride, chlorobridged anhydride, himic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and tetrabromophthalic anhydride. Acid anhydride, tetrachlorophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 5-(2,5-dioxy) Tetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, styrene maleic anhydride copolymer, etc.

It is also possible to further add compounds with oxygen capturing function etc. according to demand. Examples of compounds having an oxygen capturing function include hindered phenols, vitamin C, vitamin E, organophosphorus compounds, gallic acid, pyrogallol, and other low-molecular organic compounds that react with oxygen, or cobalt, manganese, Transition metal compounds such as nickel, iron, copper, etc.

In order to improve the adhesion to various film materials immediately after coating, xylene resin, terpene resin, phenol resin, rosin resin and other tackifiers can also be added according to the needs. When these are added, the blending amount is preferably in the range of 0.01 to 5 parts by mass relative 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 the polyester polyol (A2), active energy rays can be used as a method of reacting polymerizable carbon-carbon double bonds. As active energy rays, conventional techniques can be used, and ionizing radiation such as electron beams, ultraviolet rays, or gamma rays can be irradiated to harden them. In the case of curing with ultraviolet rays, conventional ultraviolet irradiation devices equipped with high-pressure mercury lamps, excimer lamps, metal halide lamps, etc. can be used.

In the case of irradiating ultraviolet rays to harden it, it is preferable to add light that can generate radicals and the like by ultraviolet irradiation in an amount of about 0.1 to 20 parts by mass based on 100 parts by mass of polyester polyol (A2). Polymerization) initiator.

Examples of radical-generating photo (polymerization) initiators include dehydrogenation types such as benzyl, benzophenone, Michele ketone, 2-chlorothioxanthone, and 2,4-diethylthioxanthone. , Or benzoin ether, diethoxyacetophenone, benzyl methyl ketal, hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl phenyl ketone and other photo-cracking types. Among these, it can be used individually or in combination of multiple types.

In addition, the gas barrier adhesive can also contain stabilizers (antioxidants, heat stabilizers, ultraviolet absorbers, etc.), plasticizers, antistatic agents, slip agents, anti-blocking agents, coloring agents, crystal nucleating agents, etc. . These various additives can be added to either or both of the polyol composition (A) and the polyisocyanate composition (B) in advance, or they can be mixed in the polyol composition (A) and the polyisocyanate composition ( Add when B).

The gas-barrier adhesive used in the present invention may be either a solvent type or a solvent-free type. In this specification, the solvent-based adhesive refers to a method for bonding with other substrates after applying the adhesive to the substrate and heating in an oven to volatilize the organic solvent in the coating film. The so-called dry layer The form of pressure law. Examples of solvents used include toluene, xylene, dichloromethane, tetrahydrofuran, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, acetone, methyl ethyl ketone (MEK), cyclohexanone, toluene , Xylene, n-hexane, cyclohexane, etc. Either or both of the polyol composition (A) and the polyisocyanate composition (B) contain the above-mentioned organic solvent. In the case of the solvent type, there are cases where the solvent is used as a reaction medium in the production of the constituent components of the polyol composition (A) or the polyisocyanate composition (B), and may be used as a diluent during coating.

Solvent-free adhesive refers to a method for bonding with other substrates after applying the adhesive to the substrate without heating in an oven to volatilize the solvent. The so-called solvent-free lamination method form. Neither the polyol composition (A) nor the polyisocyanate composition (B) substantially contains the above-mentioned organic solvent. The constituent components of the polyol composition (A) or the polyisocyanate composition (B), or the organic solvent used as the reaction medium in the production of its raw materials, are not cleanly removed, and the polyol composition (A) or the polyisocyanate composition (B) When a trace amount of organic solvent remains in it, it is considered that the organic solvent is not substantially contained. In addition, when the polyol composition (A) contains a low-molecular-weight alcohol, the low-molecular-weight alcohol reacts with the polyisocyanate composition (B) to become a part of the coating film, so it is not necessary to volatilize it after coating. Therefore, this form is also treated as a solvent-free adhesive.

(Sealing layer) The laminate of the present invention may have a sealing layer on the gas barrier adhesive layer. The sealing layer is a layer of heat-sealable resin that can be melted by heat and welded to each other. Examples of resins suitable for the sealing layer include polyethylene, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, polypropylene, and ethylene-vinyl acetate copolymer. Polymer, ionic polymer resin, ethylene-(meth)acrylic acid copolymer, ethylene-ethyl(meth)acrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, acrylic acid, methacrylic acid, horse Modified olefin resins, ethylene-(meth)acrylate-unsaturated carboxylic acid terpolymers made from modified olefin resins such as polyethylene or polypropylene with acetic anhydride, fumaric acid, and other unsaturated carboxylic acids , Cyclic polyolefin, cyclic olefin copolymer, polyethylene terephthalate (PET), polyacrylonitrile (PAN), etc. Films, sheets, other coating films, etc. containing one or more of these resins can be used as the sealing layer.

As the film to be the sealing layer, any of unstretched, uniaxially stretched, and biaxially stretched films can be used.

The stretched film stretched in the biaxial direction, for example, is stretched 2 to 4 times in the longitudinal direction by a roller stretcher at 50-100°C, and then stretched in the transverse direction by a tenter stretcher at 90-150°C. ~5 times, and then can be obtained by heat treatment with a tenter stretching machine in an environment of 100-240°C. Or it can also be used after simultaneous biaxial extension and successive biaxial extension.

It is also possible to use an easily peelable sealing film (easy tear film) for the sealing layer. As the easily peelable sealing film, any of an interface peeling type, a cohesive peeling type, and an interlayer peeling type can be applied, and it can be appropriately selected according to the type and required characteristics of the packaging material described later. As an index of easy peelability, it is appropriately set according to the type of packaging material and required characteristics, but as an example, the sealing strength is 2-20N/15mm. For example, the easy peelability can be expressed by mixing a phase-separated polymer of a combination of polypropylene, high-density polyethylene, low-density polyethylene, ethylene-vinyl acetate copolymer, and the like.

The film thickness of the sealing layer can be arbitrarily selected, but for example, when it is applied to a packaging material described later, it is selected within the range of 5 to 500 μm. It is more preferably 10 to 250 μm, still more preferably 15 to 100 μm. If it is less than 5 μm, sufficient lamination strength as a packaging material cannot be obtained, and there is a concern that the puncture resistance will also be reduced. If it exceeds 250 μm, the cost will increase, the film will become hard, and the workability will decrease.

(Printing layer) The laminate of the present invention may also have a printing layer as required. The position of the printing layer can be arbitrary, but as an example, it is on the surface of the substrate opposite to the gas barrier adhesive layer, or between the alumina layer and the gas barrier adhesive layer, and The aluminum oxide layer is arranged in contact with each other or through a protective coating. It can be printed with various printing inks such as gravure ink, flexographic ink, lithographic ink, stencil ink, inkjet ink, etc., and by the general printing method used in the printing of polymer films in the past. Floor.

(Layered body 　 other layers) The laminate of the present invention may have other layers as required. For example, a film may be arranged between the gas barrier adhesive layer and the sealing layer. As the film, the same ones as those exemplified as the base material can be used. Ideally use uniaxially or biaxially stretched polyester films such as polyethylene terephthalate and polyethylene naphthalate, nylon 6, nylon 66, MXD6 (poly xylylene hexamethylene diamide), etc. Uniaxially or biaxially stretched polyamide film, biaxially stretched polypropylene film, etc.

When a film is arranged between the gas barrier adhesive layer and the sealing layer, the film and the sealing layer may be bonded via the adhesive. The adhesive used at this time may be the above-mentioned gas barrier adhesive or not. The film may be bonded to the substrate via the gas barrier adhesive layer, or another layer may be further arranged between the film and the gas barrier adhesive layer.

(Method of manufacturing laminate) The laminate of the present invention can be obtained by bonding a base material provided with an alumina layer and a sealing layer by a dry lamination method or a solventless lamination method using a gas barrier adhesive. The laminated layer system has excellent gas barrier properties and can be used as a gas barrier layered body.

When the gas-barrier adhesive is solvent-based, use a roller such as a gravure roll to apply the gas-barrier adhesive on either of the base material and the sealing layer, and heat it in an oven to volatilize the organic solvent. The other is bonded together to obtain the laminate of the present invention. It is preferable to perform aging treatment after lamination. The aging temperature is preferably from room temperature to 80°C, and the aging time is preferably from 12 to 240 hours.

When the gas barrier adhesive is a solvent-free type, use a roller such as a gravure roll to apply the gas barrier adhesive heated to about 40°C to 100°C in advance on either of the base material and the sealing layer, and then apply it immediately Combine the other to obtain the laminate of the present invention. It is preferable to perform an aging treatment after lamination. The aging temperature is preferably from room temperature to 70°C, and the aging time is preferably from 6 to 240 hours.

The coating amount of the gas barrier adhesive is adjusted appropriately. In the case of a solvent type, as an example, it is adjusted ^{so that the solid content becomes 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 coating amount of the adhesive is, as an 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 materials＞ The laminate of the present invention can be used as a multilayer packaging material for the purpose of protecting foods, pharmaceuticals, and the like. When used as a multi-layer packaging material, its layer composition can be changed according to the content, use environment, and use form.

The packaging material of the present invention can be obtained by using the laminate of the present invention, stacking the sealing films of the laminate facing each other, and then heat-sealing the peripheral end of the laminate. Examples of the bag making method include bending or stacking the laminate of the present invention so that the inner layer surface (the surface of the sealing film) is opposed, and the peripheral end is sealed by, for example, a side seal type or a double seal. Type, three-sided sealing type, four-sided sealing type, envelope pasting and sealing type, palm pasting and sealing type (vertical pillow type, horizontal pillow type), ribbed seal type, flat bottom sealing type, square bottom sealing type, corner plate ( Gusset) type, other heat-sealing type and other forms for heat-sealing. The packaging material of the present invention can take various forms according to the content, use environment, and use form. It may also be a standable packaging bag (standing pouch) or the like. As a method of heat sealing, conventional methods such as rod sealing, rotating drum sealing, belt sealing, pulse sealing, high frequency sealing, and ultrasonic sealing can be performed.

The packaging material of the present invention can be filled with content from its opening, and then the opening can be heat-sealed to produce a product using the packaging material of the present invention. The filled contents include: rice crackers, bean fruits, nuts, biscuits/sweets, wafers, marshmallows, pies, half-boiled cakes, sweets, snacks and other snacks, bread, snack noodles, instant noodles , Dried noodles, pasta, aseptic packaged rice, risotto, porridge, packaged rice cake, oatmeal and other staple foods, pickles, boiled beans, natto, miso, frozen tofu, tofu, dried mushrooms, konjac, processed mountain vegetables, Processed agricultural products such as jams, peanut butter, salads, frozen vegetables, processed potato products, processed livestock products such as ham, bacon, sausages, processed chicken products, corned beef, fish ham/sausage, and aquatic products Refined products, fish plate, seaweed, soy sauce stew, bonito flakes, salted fish sausage, smoked salmon, spicy mentaiko and other processed aquatic products, peaches, tangerines, pineapples, apples, pears, cherries and other pulps, corn, Vegetables such as asparagus, mushrooms, onions, carrots, white radishes, potatoes, frozen dishes represented by hamburger meat, meatballs, seafood fried food, dumplings, croquettes, etc., prepared foods such as frozen dishes, cream, milkma Dairy products such as Lin, cheese, fresh cream, instant milk powder, formula milk powder for childcare, liquid seasonings, vacuum package curry, pet food and other foods. In addition, the packaging material of the present invention can also be used as packaging materials such as cigarettes, disposable warm packs, drip bags, and other medicines, cosmetics, and vacuum insulation materials.

Alternatively, the packaging material of the present invention may be a cover material formed using the laminate of the present invention. [Example]

Hereinafter, the present invention will be explained with examples and comparative examples, but the present invention is not limited thereto. Other values of blending composition are based on quality unless otherwise stated.

<Production of OPP film 1 with alumina layer> (Manufacturing of OPP film 1 with alumina layer) On one side of an OPP film with a thickness of 20 μm whose plane orientation coefficient Δ is adjusted to 0.011 by biaxial stretching treatment, an anchor coating agent which is a mixture of silane coupling agent, acrylic polyol and isocyanate hardener is applied to form a thickness of 0.3 μm. After the anchor coating, an aluminum oxide layer with a thickness of 15 nm was formed by electron beam heating. Hereinafter, this film is referred to as OPP film 1.

<Production of OPP film 2 with alumina layer> (Production of protective coating) A water-based protective coating was prepared by the following blending. [Coating Blending] Ion exchange water 87.67 copies Polyvinyl alcohol 8.62 copies Polyethyleneimine 0.94 copies CYMEL 385 1.80 servings Orthophosphoric acid 0.70 copies formaldehyde 0.19 parts BIOCIDE GXL 0.08 copies The prepared protective coating agent was coated on the aluminum oxide layer of OPP film 1 with a coating amount of about 0.1 g/m ² and dried at 80°C to obtain a protective coating formed on the aluminum oxide layer The OPP film. This film is also referred to as OPP film 2 below.

<Manufacturing of OPP films 3 and 4 with alumina layer> (Preparation of resin for water-based ink) In a container equipped with a thermometer, a nitrogen introduction tube, and a stirrer and replaced by nitrogen, 191 parts by mass of polyoxytetramethylene glycol (molecular weight 2000), 141 parts by mass of isophorone diisocyanate, 26 parts by mass Parts of 2,2-dimethylolpropionic acid, 28 parts by mass of 1,4-cyclohexanedimethanol, and 200 parts by mass of methyl ethyl ketone are reacted in a mixed solvent to obtain an isocyanate group at the end of the molecule. The organic solvent solution of the urethane prepolymer.

Then, by adding 20 parts by mass of a 50% potassium hydroxide aqueous solution, part or all of the carboxyl groups of the aforementioned urethane prepolymer were neutralized, and then 700 parts by mass of water and 9.0 parts by mass of 80% were added. % Hydrazine aqueous solution and fully stirred to obtain an aqueous dispersion of the urethane resin, followed by aging/removal of the solvent, to obtain an aqueous liquid ink resin with a non-volatile content of 40% by mass.

(Preparation of Aqueous Liquid Ink) The obtained resin for aqueous liquid ink was stirred and mixed with the following composition, and then kneaded in a bead mill to produce a kneaded matrix. [Kneading matrix blending] FASTPGEN BLUE LA5380 blue pigment (manufactured by DIC) 15 servings Resin for water-based liquid ink 40 servings Non-ionic pigment dispersant (manufactured by BYK) 10 servings Isopropanol 3 copies water 8 servings Silicon defoamer (manufactured by BYK) 0.2 parts

After adding 10 parts of water-based liquid ink resin and 4 parts of water to the obtained kneaded matrix, the viscosity of the water-based liquid ink was 16 seconds (25 ℃) way to add water to obtain water-based liquid ink. The water used to adjust the viscosity is 5 parts, the non-volatile content of the water-based liquid ink is 58%, and the surface tension at 25°C is 35mN/m. The surface tension is measured according to the Whihelmy method using an automatic surface tensiometer DY-300 manufactured by Kyowa Interface Science Co., Ltd. The resulting aqueous liquid ink is blended as follows. [Blend of water-based liquid ink] FASTPGEN BLUE LA5380 blue pigment (manufactured by DIC) 15 servings Resin for water-based liquid ink 50 servings Non-ionic pigment dispersant (manufactured by BYK) 10 servings Isopropanol 3 copies water 17 servings Silicon defoamer (manufactured by BYK) 0.2 parts

(Production of printed matter using OPP film) On OPP film 1, a Flexoproof100 test printer (manufactured by Testing Machines, Inc., anilox 200 lines/inch) was used to print a water-based liquid print with a full-page pattern of 240 mm in vertical x 80 mm in horizontal After the ink is applied, it is dried with a dryer, and a printing layer is provided on the aluminum oxide layer of the OPP film as the OPP film 3. The coating amount of the printing layer (the solid content of the coated aqueous liquid ink) is 1.0 g/m ² . The OPP film 2 is used instead of the OPP film 1, and a printing layer is provided on the protective coating, except that the OPP film 4 is obtained in the same manner as in the production of the OPP film 3.

＜Preparation of Adhesive＞ (Preparation of polyol composition) (EGoPA 0.9K) "Polyol A1" In a polyester reaction vessel equipped with a stirrer, a nitrogen introduction tube, a rectification tube, and a condenser, 80.12 parts of ethylene glycol, 148.12 parts of phthalic anhydride, and 0.02 parts of titanium tetraisopropoxide were added to refine The upper part of the distillation tube is slowly heated so that the temperature does not exceed 100°C to keep the internal temperature at 220°C. When the acid value becomes 1 mgKOH/g or less, the esterification reaction is terminated, and a polyester polyol "polyol A1" having a number average molecular weight of 900 and a hydroxyl value of 124.7 mgKOH/g is obtained.

(EGoPA/AA 0.5K) "Polyol A2" In a polyester reaction vessel equipped with a stirrer, nitrogen introduction tube, rectification tube, moisture separator, etc., 207.37 parts of phthalic anhydride, 184.0 parts of ethylene glycol, 87.68 parts of adipic acid and 0.014 parts of tetrahydrofuran were added. Titanium isopropoxide is slowly heated so that the temperature of the upper part of the rectifying tube does not exceed 100°C, and the internal temperature is kept at 220°C. When the acid value becomes 1 mgKOH/g or less, the esterification reaction is terminated, and a polyester polyol "polyol 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 is obtained.

(EGoPA/MA 0.6K) "Polyol A3" Add 98.1 parts of maleic anhydride, 78.5 parts of ethylene glycol and equivalent to the total amount of polycarboxylic acid and polyol in a polyester reaction vessel equipped with a mixer, nitrogen introduction pipe, rectification pipe, moisture separator, etc. 100ppm of titanium tetraisopropoxide is slowly heated so that the temperature of the upper part of the rectifying tube does not exceed 100°C, and the inner temperature is kept at 205°C. When the acid value becomes 1 mgKOH/g or less, the esterification reaction is terminated, and a polyester polyol "polyol 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 is obtained.

(EGoPA/FDCA 0.5K) "Polyol A4" Add 80.12 parts of ethylene glycol, 74.06 parts of phthalic anhydride, 78.05 parts of furandicarboxylic acid, and 0.02 parts of tetraisopropoxy to a polyester reaction vessel equipped with a stirrer, nitrogen introduction tube, rectification tube, and condenser. The base titanium is slowly heated in such a way that the temperature of the upper part of the rectifying tube does not exceed 100°C, and the internal temperature is kept at 220°C. When the acid value became 1 mgKOH/g or less, the esterification reaction was terminated, and a polyester polyol "polyol 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 was obtained.

(GLY(EGoPA)3) "Polyol A5" Add 92.09 parts of glycerol, 444.36 parts of phthalic anhydride, 186.21 parts of ethylene glycol, and 0.07 parts of tetraisopropyl in a polyester reaction vessel equipped with a stirrer, nitrogen introduction tube, rectification tube, and condenser. Titanium oxide is slowly heated so that the temperature of the upper part of the rectifying tube does not exceed 100°C, and the internal temperature is kept at 220°C. When the acid value becomes 1 mgKOH/g or less, the esterification reaction is terminated, and a polyester polyol "polyol 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 is obtained.

(GLY(EGoPA)3+MICA)「Polyol A6」 Add 70 parts of "polyol A5" to a container equipped with a blender, and heat and stir at 90°C to make the polyol fully maintain its fluidity. While stirring, add 30 parts of HM6025 (manufactured by Henghao, natural mica/non-swellable, plate shape, average particle size 10μm, aspect ratio 100 or more), and stir at 90°C until uniform. By cooling this, "polyol A6" in which an inorganic compound is dispersed in "polyol A5" is obtained.

(EGoPA/AA 0.5K+MICA) "Polyol A7" Add 70 parts of "polyol A2" to a container equipped with a blender, and heat and stir at 90°C to make the polyol fully maintain its fluidity. While stirring, add 30 parts of HM6025 (manufactured by Henghao, natural mica/non-swellable, plate shape, average particle size 10μm, aspect ratio 100 or more), and stir at 90°C until uniform. By cooling this, "polyol A7" in which an inorganic compound is dispersed in "polyol A2" is obtained.

(DEGAA06K) "Polyol A8" Add 164.73 parts of diethylene glycol, 146.14 parts of adipic acid and 0.02 parts of titanium tetraisopropoxide into a polyester reaction vessel equipped with a stirrer, nitrogen introduction tube, rectification tube, and condenser to rectify The upper part of the tube is slowly heated so that the temperature does not exceed 100°C to keep the internal temperature at 220°C. When the acid value becomes 1 mgKOH/g or less, the esterification reaction is terminated, and a polyester polyol "polyol A8" having a number average molecular weight of 600, a hydroxyl value of 187.0 mgKOH/g, and an acid value of 0.8 mgKOH/g is obtained.

(DEGAA2.0K) "Polyol A9" Add 125.33 parts of diethylene glycol, 146.14 parts of adipic acid and 0.02 parts of titanium tetraisopropoxide to a polyester reaction vessel equipped with a stirrer, nitrogen introduction tube, rectification tube, and condenser to rectify The upper part of the tube is slowly heated so that the temperature does not exceed 100°C to keep the internal temperature at 220°C. When the acid value became 1 mgKOH/g or less, the esterification reaction was terminated, and a polyester polyol "polyol A9" 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 was obtained.

(DEG/AA 0.6K+MICA) "Polyol A10" Add 70 parts of "polyol A8" to a container equipped with a blender, and heat and stir at 90°C to make the polyol fully maintain its fluidity. While stirring, add 30 parts of HM6025 (manufactured by Henghao, natural mica/non-swellable, plate shape, average particle size 10μm, aspect ratio 100 or more), and stir at 90°C until uniform. By cooling this, "polyol A10" in which an inorganic compound is dispersed in "polyol A8" is obtained.

(DEG/AA 2.0K+MICA) "Polyol A11" Add 70 parts of "polyol A9" to a container equipped with a blender, and heat and stir at 90°C to make the polyol fully maintain its fluidity. While stirring, add 30 parts of HM6025 (manufactured by Henghao, natural mica/non-swellable, plate shape, average particle size 10μm, aspect ratio 100 or more), and stir at 90°C until uniform. By cooling this, "polyol A11" in which an inorganic compound is dispersed in "polyol A9" is obtained.

(Preparation of polyisocyanate composition) "Hardener B1" Add 80.12 parts of ethylene glycol, 148.12 parts of phthalic anhydride, and 0.02 parts of tetraisopropoxide titanium to a polyester reaction vessel equipped with a stirrer, nitrogen introduction tube, rectification tube, and condenser to rectify The upper part of the tube is slowly heated so that the temperature does not exceed 100°C to keep the internal temperature at 220°C. When the acid value becomes 1 mgKOH/g or less, the esterification reaction is terminated, and a polyol intermediate with a number average molecular weight of 400 is obtained. Next, 71.45 parts of phenyl dimethyl diisocyanate and 46.26 parts of Millionate MN (4,4'-diphenyl) were added to a reaction vessel equipped with a stirrer, a nitrogen introduction tube, a rectification tube, a cooling condenser, and a dropping funnel. Mixture of methyl methane diisocyanate and 2,4'-diphenylmethane diisocyanate), stir while heating at 70°C, use a dropping funnel to drop 73.82 parts of the polyol intermediate in 2 hours, and stir for another 4 hours , The "hardener B1" as a polyisocyanate was obtained. The NCO% measured in accordance with JIS-K1603 is 15.1%.

"Hardener B2" In a reaction vessel equipped with a stirrer, a nitrogen introduction tube, a rectification tube, a cooling condenser, and a dropping funnel, 71.45 parts of phenyl dimethyl diisocyanate and 46.26 parts of Millionate MN (4,4'-diphenyl Mixture of methane diisocyanate and 2,4'-diphenylmethane diisocyanate), stir while heating to 70°C, using a dropping funnel, drop 92.28 parts of "polyol A2" over 2 hours, and stir for 4 hours , The "hardener B2" as a polyisocyanate was obtained. The NCO% measured in accordance with JIS-K1603 is 15.1%.

"Hardener B3" Add 24.72 parts of ethylene glycol, 60.10 parts of diethylene glycol, 2.49 parts of neopentyl glycol, and 125.3 parts of adipic acid to a polyester reaction vessel equipped with a mixer, nitrogen introduction tube, rectification tube, and condenser. And 0.02 parts of titanium tetraisopropoxide, slowly heating so that the temperature of the upper part of the rectifying tube does not exceed 100°C, keeping the internal temperature at 220°C. When the acid value becomes 1 mgKOH/g or less, the esterification reaction is terminated, and an intermediate is obtained. Put 83.45 parts of Millionate MT and 83.5 parts of Lupranate MI into a reaction vessel equipped with a stirrer, nitrogen introduction tube, cooling condenser, and dropping funnel, and stir while heating to 70°C. Use the dropping funnel to slowly drip over 2 hours. The intermediate was further stirred for 4 hours to obtain "hardener B3" as a polyisocyanate. The NCO% measured in accordance with JIS-K1603 is 13.2%.

"Hardener B4" In a reaction vessel equipped with a stirrer, a nitrogen introduction tube, a rectification tube, a cooling condenser, and a dropping funnel, 71.45 parts of phenyl dimethyl diisocyanate and 46.26 parts of Millionate MN (4,4'-diphenyl Mixture of methane diisocyanate and 2,4'-diphenylmethane diisocyanate), stir while heating to 70°C, using a dropping funnel, drop 92.28 parts of "polyol A4" over 2 hours, and stir for 4 hours , Get "hardener B4". The NCO% measured in accordance with JIS-K1603 is 15.1%.

"Hardener B5" Add 570.41 parts of Millionate MI to a reaction vessel equipped with a stirrer, a nitrogen inlet tube, a cooling condenser, and a dropping funnel, and stir while heating to 70°C. Use the dropping funnel to slowly drop 597.00 parts of PPG1000 over 2 hours, and then It stirred for 4 hours to obtain "hardener B5" as a polyisocyanate. The NCO% measured in accordance with JIS-K1603 is 13.5%.

"Hardener B6" Mitsui Chemicals "TAKENATE D-110N" (trimethylolpropane adduct of xylylene diisocyanate, 75.0% non-volatile content, 11.5% NCO%) is made in a ratio of 50/50 (mass ratio). ) It is mixed with Mitsui Chemicals "TAKENATE 500" (non-volatile content of m-phthaloyl diisocyanate> 99%, NCO% 44.6%) and used as "hardener B6" The non-volatile content of hardener B1 is 87.5%, and the NCO% is 28.05%.

"Hardener B7" Use "PASLIM VM108CP" manufactured by DIC Co., Ltd. as "hardener B7".

(Preparation of Adhesive) (Example 1)-(Example 14) The prepared polyols and polyisocyanates were blended in the proportions shown in Tables 1 to 2 to obtain the adhesives of Examples 1-14.

(Comparative Example 1)-(Comparative Example 4) The prepared polyol and polyisocyanate were blended in the ratio shown in Table 3 to obtain the adhesive of Comparative Example 1-4.

<Adhesive coating method> (Method 1) Using the bar coating method, apply the prepared adhesives on the alumina layer of OPP film 1 ^{so that the coating film amount becomes 3.0g/m 2 (solid content).} , On the protective coating of OPP film 2 and on the printed layers of OPP films 3 and 4, use a dryer set at 70°C to volatilize the dilution solvent to dry. Next, the adhesive surfaces of OPP films 1 to 4 coated with the aforementioned adhesive were bonded to an LLDPE film (TUX-HC manufactured by Mitsui Chemicals Tohcello, thickness 40 μm). The aging treatment was performed at 40°C/2 days to obtain a laminate.

(Method 2) Heat the prepared adhesive to about 70°C, and use a solvent-free test coater to coat the alumina of OPP film 1 ^{with a coating amount of 2.5 g/m 2 (solid content)} On the upper layer, the protective coating of OPP film 2, and the printed layer of OPP films 3 and 4, the adhesive side of OPP films 1 to 4 coated with the aforementioned adhesive and the LLDPE film (TUX-HC, manufactured by Mitsui Chemicals Tohcello, Thickness 40μm) bonding. The aging treatment was performed at 40°C/2 days to obtain a laminate.

(Reference example) Apply the prepared adhesive to the flat surface by biaxial stretching by the method in the table (method 1 or method 2 above) so that the coating amount becomes 5.0g/m ^{2 (solid content)} The orientation coefficient Δ was adjusted to 0.011 on one side of the OPP film with a thickness of 20 μm, and the adhesive side of the OPP film coated with the adhesive was bonded to the CPP film (ZK207 manufactured by Toray Advanced Film, 70 μm). The aging treatment was performed at 40°C/2 days to obtain a laminate of the reference example.

<Evaluation> (Oxygen permeability) Adjust the aging treatment to the size of 10cm×10cm, using OX-TRAN2/21 (manufactured by MOCON: oxygen permeability measuring device), in accordance with JIS-K7126 (isobaric Method), the oxygen transmission rate (OTR) was measured under an environment of 23°C and 0%RH. The unit is cc/m ² ･day･atm. In addition, RH represents humidity. The results are summarized in Tables 1-3.

(Oxygen penetration rate after bending test) Adjust the aging treatment to the size of 30cm×20cm, according to ASTM F392, using Gelvo flex tester (BE-1006 Gelvo flex tester with thermostatic bath, TESTER SANGYO Co., Ltd. ) Perform a bending test. In addition, the bending test was performed at 440°/90mm, linear motion 65mm, and 23°C under the condition of 5 bending times, and the oxygen transmission rate after Gelvo flex treatment (OTR after bending test) was measured. The unit is cc/m ² ･day･atm. The results are summarized in Tables 1-3.

(Water vapor transmission rate) Using the water vapor transmission rate measuring device 7002 manufactured by Systech Illinois, the water vapor transmission rate of the laminated body after the aging treatment is measured by the isobaric method under the environment of 40℃ and 90%RH. Rate (MVTR). The unit is g/m ² ･day. In addition, RH means humidity. The results are summarized in Tables 1-3.

(Water vapor transmission rate after bending test) Adjust the aging treatment to the size of 30cm×20cm, according to ASTM F392, with Gelvo flex tester (BE-1006 Gelvo flex tester with constant temperature bath, TESTER SANGYO limited Company) conduct a bending test. In addition, the bending test was performed at 440°/90mm, linear motion 65mm, 23°C, under the condition of 5 bending times, and the water vapor transmission rate after Gelvo flex treatment (MVTR after bending test) was measured. The unit is g/m ² ･day. The results are summarized in Tables 1-3.

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Coating method 1 1 1 1 2 2 2 Polyol A1 100 100 Polyol A2 Polyol A3 40 38 38 Polyol A4 100 Polyol A5 100 Polyol A6 Polyol A7 Hardener B1 100 Hardener B2 100 Hardener B3 Hardener B4 87.5 100 Hardener B6 33.42 67.2 33.42 Hardener B7 Methyl ethyl ketone 125 150 188 125 Triacetylglycerol Reference example: OPP/CPP laminate (adhesive coating amount 5g/m ² ) OTR 60 26 45 40 120 100 75 Evaluation results of OPP film 1/AD/PE laminate OTR 0.53 0.25 0.41 0.37 0.95 0.82 0.65 MVTR 0.5 0.4 0.4 0.4 0.53 0.5 0.54 OTR after bending test 0.65 0.37 0.53 0.49 1.07 0.94 0.77 MVTR after bending test 0.55 1.2 0.4 0.6 0.6 0.6 0.55 Evaluation results of OPP film 2 (OPP film 1/OC)/AD/PE laminate OTR 0.43 0.15 0.31 0.27 0.85 0.72 0.55 MVTR 0.5 0.4 0.4 0.4 0.53 0.5 0.54 OTR after bending test 0.55 0.27 0.43 0.39 0.97 0.84 0.67 MVTR after bending test 0.55 0.6 0.4 0.61 0.61 0.6 0.55 Evaluation results of OPP film 3 (OPP film 1/printing layer)/AD/PE laminate OTR 0.6 0.32 0.48 0.44 1.02 0.89 0.72 MVTR 0.6 0.5 0.5 0.5 0.63 0.6 0.64 OTR after bending test 0.75 0.47 0.63 0.59 1.17 1.04 0.87 MVTR after bending test 0.8 0.7 0.7 0.7 0.83 0.8 0.84 Evaluation results of OPP film 4 (OPP film 1/OC/printing layer)/AD/PE laminate OTR 0.43 0.15 0.31 0.27 0.85 0.72 0.55 MVTR 0.51 0.4 0.4 0.42 0.53 0.51 0.55 OTR after bending test 0.6 0.3 0.45 0.44 1 0.84 0.67 MVTR after bending test 0.55 0.6 0.41 0.63 0.6 0.62 0.55

[Table 2] Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Coating method 2 2 1 1 1 1 2 Polyol A1 Polyol A2 62 75 Polyol A3 Polyol A4 Polyol A5 100 100 Polyol A6 100 100 Polyol A7 38 Hardener B1 Hardener B2 100 100 Hardener B3 100 40 Hardener B4 Hardener B6 28 Hardener B7 37.5 26.25 Methyl ethyl ketone 128 140 128 140 Triacetylglycerol 8 2 Reference example: OPP/CPP laminate (adhesive coating amount 5g/m ² ) OTR 280 140 90 180 40 20 50 Evaluation results of OPP film 1/AD/PE laminate OTR 1.58 1.07 0.76 1.28 0.37 0.19 0.45 MVTR 0.7 0.55 0.5 0.6 0.3 0.3 0.36 OTR after bending test 1.8 1.19 0.88 1.4 0.49 0.31 0.57 MVTR after bending test 0.9 0.62 0.55 0.7 0.4 0.9 0.5 Evaluation results of OPP film 2 (OPP film 1/OC)/AD/PE laminate OTR 1.48 0.97 0.54 1.18 0.27 0.09 0.35 MVTR 0.7 0.55 0.5 0.6 0.3 0.3 0.36 OTR after bending test 1.58 1.09 0.6 1.3 0.39 0.21 0.47 MVTR after bending test 0.9 0.62 0.55 0.7 0.4 0.9 0.5 Evaluation results of OPP film 3 (OPP film 1/printing layer)/AD/PE laminate OTR 1.68 1.14 0.83 1.35 0.44 0.26 0.52 MVTR 0.8 0.65 0.6 0.7 0.4 0.4 0.46 OTR after bending test 1.78 1.29 0.98 1.5 0.59 0.41 0.67 MVTR after bending test 1 0.85 0.8 0.9 0.6 0.6 0.66 Evaluation results of OPP film 4 (OPP film 1/OC/printing layer)/AD/PE laminate OTR 1.48 1 0.54 1.18 0.27 0.11 0.35 MVTR 0.7 0.55 0.5 0.6 0.3 0.3 0.28 OTR after bending test 1.58 1.12 0.61 1.3 0.39 0.24 0.5 MVTR after bending test 0.92 0.63 0.57 0.74 0.42 0.98 0.52

[table 3] Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Coating method 2 1 2 1 Polyol A8 50 Polyol A9 100 Polyol A10 50 Polyol A11 100 Hardener B1 Hardener B5 100 70 Hardener B6 13.9 7.11 Hardener B7 Methyl ethyl ketone 100 100 Triacetylglycerol Reference example: OPP/CPP laminate (adhesive coating amount 5g/m ² ) OTR 800 700 400 400 Evaluation results of OPP film 1/AD/PE laminate OTR 2.4 2.3 2.3 2.3 MVTR 1.2 1.2 1.1 1.1 OTR after bending test 4.1 4 4 4 MVTR after bending test 1.4 1.4 1.3 1.3 Evaluation results of OPP film 2 (OPP film 1/OC)/AD/PE laminate OTR 2.2 2.1 2.1 2.1 MVTR 1.2 1.2 1.1 1.1 OTR after bending test 3.1 3 3 3 MVTR after bending test 1.4 1.4 1.4 1.4 Evaluation results of OPP film 3 (OPP film 1/printing layer)/AD/PE laminate OTR 2.4 2.3 2.3 2.3 MVTR 1.2 1.2 1.1 1.1 OTR after bending test 4.1 4 4 4 MVTR after bending test 1.4 1.4 1.3 1.3 Evaluation results of OPP film 4 (OPP film 1/OC/printing layer)/AD/PE laminate OTR 2.2 2.1 2.1 2.1 MVTR 1.2 1.2 1.1 1.1 OTR after bending test 3 2.9 2.9 2.7 MVTR after bending test 1.4 1.4 1.4 1.4

It is clear from the examples and comparative examples that the laminate of the present invention has reduced oxygen and water vapor permeability, has excellent barrier properties, and maintains these characteristics even after a bending test. On the other hand, the laminates of Comparative Examples 1 to 4 had poor gas barrier properties, especially oxygen permeability exceeding 2 cc, and the performance after the bending test was markedly deteriorated.

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Claims (5)

A laminated body having: Substrates containing biaxially stretched polypropylene, The alumina layer disposed on the aforementioned substrate, and A gas barrier adhesive layer arranged on the aforementioned alumina layer. The laminate of claim 1, which has a coating layer disposed between the alumina layer and the gas barrier adhesive layer. Such as the laminate of claim 1 or 2, which has an anchor coating layer disposed between the substrate and the alumina layer. The laminate according to any one of claims 1 to 3, which has a printed layer disposed between the coating layer and the gas barrier adhesive layer. A packaging material comprising the laminated body as claimed in any one of claims 1 to 4.