JP2021070311A - Laminate and package using the same - Google Patents

Abstract

To provide a laminate having a high barrier property and excellent in a hand tearability and a dead hold property and also to provide a package using the same.SOLUTION: A laminate 10 includes: a paper substrate layer 11; a sealant layer 12 arranged on one side of the paper substrate layer 11 and having a metal or inorganic oxide vapor-deposited layer 13; and a barrier adhesive layer 14 arranged between the paper substrate layer 11 and the vapor-deposited layer 13 and bonding the paper substrate layer 11 and the vapor-deposited layer 13. The laminate has an oxygen permeation rate of 3.0 cc/m2/day/atm or less measured at 23°C and 90%RH in accordance with JIS K 7126-2 and satisfies 1.0≤t1/t2≤5.0 if a mass of the paper substrate layer 11 per 1 m2 is t1 and a mass of the sealant layer 12 having the vapor-deposited layer 13 per 1 m2 is t2.SELECTED DRAWING: Figure 1

Description

The present invention relates to a laminate having a paper base material layer and a sealant layer provided with a vapor-deposited layer, and a package using the same.

Conventionally, a laminate packaging material using a paper base material layer that requires barrier properties is, for example, a resin film (for example, aluminum) having a vapor-deposited layer such as metal between the paper base material layer and the sealant layer. It is known that a vapor-deposited PET (polyethylene terephthalate) resin film) or the like is laminated and arranged (see, for example, Patent Document 1).
However, although the barrier property can be sufficiently ensured in the laminated body packaging material having such a structure, a stretched resin film such as PET, which is a base material of the vapor deposition layer, is interposed as an intermediate layer. Therefore, for example, this laminated body When used as a packaging body such as a packaging bag, there is a problem that hand-cutting property and dead-holding property (shape retention property) are poor.

Japanese Unexamined Patent Publication No. 2008-094426

An object of the present invention is to provide a laminated body having a high barrier property and excellent hand-cutting property and dead-holding property, and a packaging body using the same, in order to solve the above-mentioned problems.

The present invention solves the above problems by the following solutions. In addition, in order to facilitate understanding, the description will be given with reference numerals corresponding to the embodiments of the present invention, but the present invention is not limited thereto.

The first invention includes a paper base material layer, a sealant layer provided on one surface side of the paper base material layer and having a vapor deposition layer of a metal or an inorganic oxide, and the paper base material layer and the vapor deposition layer. The paper base material layer and the barrier adhesive layer for joining the vapor deposition layer are provided between the two, and the oxygen permeability measured at 23 ° C. and 90% RH according to JIS K 7126-2 is 3. When it is 0.0 cc / m ² / day / atm or less and ^{the mass per 1 m 2 of the paper substrate layer is t1 and the mass per 1 m 2 of the} sealant layer including the vapor-deposited layer is t2, 1 It is a laminated body satisfying 0.0 ≦ t1 / t2 ≦ 5.0.

The second invention is the laminate of the first invention in which the basis weight of the paper base material layer is 30 g / m ² or more and 100 g / m ^{2 or less.}

In the third invention, the sealant layer is a laminate of the first invention or the second invention having a thickness of 20 μm or more.

In the fourth invention, the sealant layer is a laminate of any of the first to third inventions, which is an unstretched polyolefin resin film.

In the fifth invention, the unstretched polyolefin resin film is an unstretched polypropylene resin film, and the unstretched polypropylene resin film is a laminate of the fourth invention containing biomass polyethylene.

In the sixth invention, the barrier adhesive layer is a cured product of a resin composition containing a resin having two or more hydroxyl groups in one molecule and an isocyanate compound having two or more isocyanate groups in one molecule. The laminate according to any one of the first to fifth inventions, wherein the main skeleton of the resin is polyester or polyester polyurethane, and the ortho-oriented aromatic dicarboxylic acid or its anhydride is contained as a polyester constituent monomer component. Is.

The seventh invention is a package formed by using any of the laminates from the first invention to the sixth invention.

According to the present invention, it is possible to provide a laminated body having high barrier properties and excellent hand-cutting property and dead-holding property, and a packaging body using the same.

It is sectional drawing of the laminated body of embodiment. It is a figure which shows the example of the package using the laminated body of an embodiment. It is a figure which shows another example of the package using the laminated body of an embodiment. It is a figure which shows another example of the package using the laminated body of an embodiment. It is a figure which shows another example of the package using the laminated body of an embodiment. It is a figure which shows another example of the package using the laminated body of an embodiment.

The laminate according to the present invention will be described with reference to the drawings. FIG. 1 shows an example of a cross-sectional view of the laminated body according to the present invention.
<Laminated body of the embodiment>
The laminate 10 is, for example, a packaging material used for packaging foods and the like. As shown in FIG. 1, the laminate 10 of the embodiment, which is an example of the present invention, is a sealant layer 12 including a paper base layer 11 and a vapor deposition layer 13 provided on one surface side of the paper base layer 11. And a barrier adhesive layer 14 having a barrier property for joining the vapor deposition layer 13 and the paper base material layer 11. That is, in the laminated body 10, the paper base material layer 11, the barrier adhesive layer 14, the vapor deposition layer 13, and the sealant layer 12 are sequentially laminated.
Hereinafter, each layer constituting the laminated body 10 will be described.

(Paper substrate layer)
The paper base material layer 11 is a base material layer that supports the sealant layer 12 including the vapor deposition layer 13, and is ^{a cup base paper for a paper cup having a basis weight of more than 100 g / m 2} and a milk carton base paper for a paper container. Unlike, it is a paper base material that constitutes a flexible, so-called flexible paper packaging. Specifically, the basis weight of the paper substrate layer ^{is preferably 30 g / m 2} or more and 100 g / m ² or less, and more preferably 35 g / m ² or more and 70 g / m ² or less. When the basis weight of the paper base material layer is 30 g / m ² or more and 100 g / m ² or less, the mechanical strength is strong, and it has excellent hand-cutting property and dead hold property, and can be used as a packaging body such as a packaging bag. Has flexibility. Examples of the paper base material layer 11 include kraft paper, woodfree paper, coated paper, and paper having barrier properties (barrier coated paper).

Here, a pattern layer and a surface layer may be sequentially provided on the surface of the paper base material layer 11 opposite to the barrier adhesive layer 14.
(Pattern layer)
The pattern layer is a printing layer provided on the surface of the paper base material layer 11 opposite to the barrier adhesive layer 14 and on which a pattern is printed. Here, the pattern is a recording target of various modes that can be recorded or printed on the paper base material layer 11, and is not particularly limited, and is not particularly limited, and is not particularly limited, such as a figure, a character, a pattern, a pattern, a symbol, a pattern, and a mark. Widely includes. In particular, when the laminate 10 is used for a packaging body such as a packaging bag intended to contain food, a drawing of the contents, a product name of the contents, an expiration date, a manufacturing date, and a serial number are used as patterns. Characters indicating information such as are used.

(Surface layer)
The surface layer is a layer provided on the pattern layer, and is a layer located on the outermost side of the container when the laminated body 10 is used for a packaging body such as a packaging bag. The surface layer is formed of, for example, an overprint varnish (OP varnish), and can suppress disappearance of the pattern layer due to rubbing or the like, or suppress falsification of the pattern.
In the above description, an example in which the pattern layer and the surface layer are sequentially provided on the paper base material layer 11 has been described, but the pattern layer and the surface layer may be omitted as necessary.

(Sealant layer)
The sealant layer 12 is a layer exposed on the surface of the laminate 10 opposite to the paper base material layer 11. The sealant layer 12 is the innermost layer when a package such as a packaging bag is formed by using the laminated body 10, and has a heat-sealing property having adhesive properties by heating. Further, the sealant layer 12 includes a vapor deposition layer 13 on the paper base material layer 11 side. Details of the vapor deposition layer 13 will be described later.

As the resin film constituting the sealant layer 12, an unstretched polyolefin resin film having a heat-sealing property is preferably used. In particular, in the present invention, an unstretched polyethylene-based resin film or an unstretched polypropylene-based resin film can be preferably used.

Examples of the resin constituting the unstretched polyethylene-based resin film include low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), and linear low-density polyethylene (LLDPE). Not only these homopolymers, but also a copolymerized polyolefin in which a part of ethylene is replaced with another monomer may be used.

Here, high density polyethylene refers to polyethylene having a density greater than 0.942 g / cm ^3, medium density polyethylene refers to polyethylene having a density of 0.942 g / cm ³ or less exceed 0.925 g / cm ³ .. Further, the low-density polyethylene can also be referred to as a high-pressure method low-density polyethylene, which is a high-pressure method ethylene homopolymer, which can be obtained by a conventionally known high-pressure radical polymerization method, and has a density of ^{0.925 g / cm 3 or less.} It is polyethylene to have. Further, the linear low-density polyethylene is a copolymer of ethylene and α-olefin polymerized using a multisite catalyst represented by a Ziegler-Natta catalyst or a single site catalyst represented by a metallocene catalyst. , Polyethylene having a density of 0.925 g / cm ³ or less.
In the present invention, the density is measured from a method based on JIS K7112.

Examples of the resin constituting the unstretched polypropylene-based resin film (CPP film) include homopolypropylene, random polypropylene, and block polypropylene. It may be a copolymerized polypropylene in which a part of propylene is replaced with another monomer.

Further, the polypropylene-based resin film may contain polyethylene, and it is desirable that the polyethylene contained therein contains plant-derived biomass polyethylene. Here, when the unstretched polypropylene-based resin film contains biomass polyethylene, it is desirable that the biomass polyethylene is contained in the range of 5 to 30 parts by mass with respect to 100 parts by mass of the polypropylene-based resin.

<Biomass-derived ethylene>
The method for producing biomass-derived ethylene, which is a raw material for biomass polyethylene, is not particularly limited, and can be obtained by a conventionally known method. Hereinafter, an example of a method for producing ethylene-derived ethylene will be described.

Biomass-derived ethylene can be produced using biomass-derived ethanol as a raw material. In particular, it is preferable to use fermented ethanol derived from biomass obtained from plant raw materials. The plant material is not particularly limited, and conventionally known plants can be used. For example, corn, sugar cane, beets, and manioc can be used.

Biomass-derived fermented ethanol refers to ethanol that has been purified after being produced by contacting a culture solution containing a carbon source obtained from a plant material with a microorganism that produces ethanol or a product derived from a crushed product thereof. For the purification of ethanol from the culture broth, conventionally known methods such as distillation, membrane separation, and extraction can be applied. For example, a method such as adding benzene, cyclohexane or the like and azeotropically boiling the mixture, or removing water by membrane separation or the like can be applied.

In order to obtain the above ethylene, advanced purification such as reducing the total amount of impurities in ethanol to 1 ppm or less may be performed at this stage.

A catalyst is used when ethylene is obtained by a dehydration reaction of ethanol, but the catalyst is not particularly limited, and conventionally known catalysts can be used. Advantageous in the process is a fixed bed flow reaction in which the catalyst and the product can be easily separated, and for example, γ-alumina and the like are preferable.

Since this dehydration reaction is an endothermic reaction, it is usually carried out under heating conditions. If the reaction proceeds at a commercially useful reaction rate, the heating temperature is not limited, but is preferably 100 ° C. or higher, more preferably 250 ° C. or higher, still more preferably 300 ° C. or higher. The upper limit is not particularly limited, but from the viewpoint of energy balance, equipment, etc., 500 ° C. or lower is preferable, and 400 ° C. or lower is more preferable.

In the dehydration reaction of ethanol, the yield of the reaction depends on the amount of water contained in the ethanol supplied as a raw material. Generally, when a dehydration reaction is carried out, it is preferable that there is no water in consideration of the efficiency of removing water. However, in the case of the dehydration reaction of ethanol using a solid catalyst, it was found that the amount of other olefins, especially butene, tends to increase in the absence of water. It is presumed that it is not possible to suppress ethylene dimerization after dehydration without the presence of a small amount of water. The lower limit of the allowable water content is 0.1% by mass or more, preferably 0.5% by mass or more. The upper limit is not particularly limited, but from the viewpoint of mass balance and heat balance, 50% by mass or less is preferable, 30% by mass or less is more preferable, and 20% by mass or less is further preferable.

By performing the ethanol dehydration reaction in this way, a mixed portion of ethylene, water and a small amount of unreacted ethanol can be obtained, but since ethylene is a gas at about 5 MPa or less at room temperature, gas-liquid separation is performed from these mixed portions. Ethylene can be obtained by removing water and ethanol. This can be done by a known method.

Ethylene obtained by gas-liquid separation is further distilled, and the distillation method, operating temperature, residence time, and the like are not particularly limited except that the operating pressure at this time is normal pressure or higher.

When the raw material is ethanol derived from ammonia, the obtained ethylene contains carbonyl compounds such as ketones, aldehydes, and esters, which are impurities mixed in the ethanol fermentation process, carbon dioxide gas, which is a decomposition product thereof, and decomposition products of enzymes. It contains a very small amount of nitrogen-containing compounds such as amines and amino acids, which are impurities, and ammonia, which is a decomposition product thereof. Depending on the use of ethylene, these trace amounts of impurities may cause a problem and may be removed by purification. The purification method is not particularly limited, and can be performed by a conventionally known method. As a suitable purification operation, for example, an adsorption purification method can be mentioned. The adsorbent used is not particularly limited, and conventionally known adsorbents can be used. For example, a material having a high surface area is preferable, and the type of adsorbent is selected according to the type and amount of impurities in ethylene obtained by the dehydration reaction of ethanol derived from biomass.

In addition, caustic water treatment may be used in combination as a method for purifying impurities in ethylene. When caustic water treatment is performed, it is desirable to perform it before adsorption purification. In that case, it is necessary to perform a water removal treatment after the caustic treatment and before the adsorption purification.

<Biomass polyethylene>
Biomass polyethylene is obtained by polymerizing a monomer containing ethylene derived from biomass. As the biomass-derived ethylene, it is preferable to use the ethylene obtained by the above-mentioned production method. Since ethylene derived from biomass is used as the monomer as a raw material, the polyethylene polymerized is derived from biomass. Examples of the biomass polyethylene include biomass linear low-density polyethylene manufactured by Braskem (trade name: SLL318, density: 0.918 g / cm ³ (918 kg / m ³ ), MFR: 2.7 g / 10 minutes, biomass degree. 87%), Biomass low-density polyethylene manufactured by Braskem (trade name: SEB853, density: 0.923 g / cm ³ (923 kg / m ³ ), MFR: 2.7 g / 10 minutes, biomass degree 95%), etc. are used. be able to. The raw material monomer for polyethylene does not have to contain 100% by mass of ethylene derived from biomass.
In the present invention, the melt flow rate (MFR) is measured in accordance with JIS K6921 (190 ° C.).

As long as the object of the present invention is not impaired, the monomer as a raw material of biomass polyethylene may further contain ethylene derived from fossil fuel.

Since carbon dioxide in the atmosphere contains C14 at a fixed ratio (105.5 pMC), the C14 content in plants that grow by taking in carbon dioxide in the atmosphere, for example, corn, is also about 105.5 pMC. It is known that there is. It is also known that fossil fuels contain almost no C14. Therefore, the proportion of biomass-derived carbon can be calculated by measuring the proportion of C14 contained in all carbon atoms. In the present invention, the "biomass degree" indicates the weight ratio of the biomass-derived component. Hereinafter, unless otherwise specified, the "biomass degree" shall indicate the weight ratio of the biomass-derived components.

In the present invention, theoretically, if all biomass-derived ethylene is used as the raw material for polyethylene, the biomass-derived ethylene concentration is 100%, and the biomass degree of biomass polyethylene is 100%. Further, the biomass-derived ethylene concentration in the fossil fuel polyethylene produced only from the fossil fuel-derived raw material is 0%, and the biomass degree of the fossil fuel polyethylene is 0%.

In the present invention, the biomass polyethylene or the resin layer derived from biomass does not need to have a biomass degree of 100%. This is because if a raw material derived from biomass is used even in a part of the resin film, it is in line with the purpose of reducing the amount of fossil fuel used as compared with the conventional case.

The resin film (sealant layer 12) preferably has a biomass degree of 5% or more. As a result, the environmental load reduction property can be further improved. The biomass degree of the resin film is more preferably 5% or more and 90% or less, further preferably 5% or more and 50% or less, and even more preferably 10 or more and 25% or less.

The unstretched polyolefin resin film may be a single layer or a multilayer. When the unstretched polyolefin resin film is formed into a film, for example, the film's workability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, releasability, flame retardancy, etc. Various plastic compounding agents and additives can be added for the purpose of improving and modifying antifungal properties, electrical properties, strength, etc., and the amount of addition can be from a very small amount to several tens of percent. , Can be arbitrarily added depending on the purpose. Examples of general additives include cross-linking agents, antioxidants, ultraviolet absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, modifying resins and the like.

The surface of the unstretched polyolefin resin film on the side where the vapor deposition layer is formed may be subjected to surface treatment described in detail later.

The unstretched polyolefin resin film is a method of independently forming the above-mentioned various resins by using a film-forming method such as an extrusion method, a cast molding method, a T-die method, a cutting method, an inflation method, or the like. By known means such as a method of forming a multi-layer co-extrusion film using various resins of more than one kind, and a method of using two or more kinds of resins and mixing them before forming a film to form a film. Obtainable.

Further, as the resin film constituting the sealant layer 12, instead of the unstretched polyolefin resin film, a biodegradable polylactic acid (PLA) resin or polybutylene succinate (PBS) resin can be used.

<Polylactic acid (PLA) resin>
For example, the sealant layer 12 may be made of a polylactic acid resin. The polylactic acid resin is, for example, a polymer containing L-, D-, or DL-lactic acid units as a main component, and uses a biodegradable polyester having transparency and similar physical characteristics to a soft type polyolefin resin. can do.

The above polylactic acid resin has a melt flow rate (MFR) in the range of 1.0 to 20.0 g / 10 minutes, preferably 1.5 to 12.0 g / 10 minutes (190 ° C., 2.16 kg). The density is in the range of about 1.10 to 1.30 g / cm ³ , the melting point is in the range of 150 to 170 ° C., and in the amorphous type, it is in the range of Tg = 50 to 70 ° C. Can be preferably used.

Basically, the polylactic acid resin has relatively softness, is melted by heat, has heat sealability, and is excellent in melt tension and stretchability, and is suitable for coextrusion molding, which will be described later. Therefore, it is possible to use the polylactic acid resin alone, but from the viewpoint of improving the flexibility, it is preferable to add a softening modifier to the extent that the function of the sealant layer 12 is not impaired. When the softening modifier is added, the polylactic acid resin and the softening modifier are preferably kneaded in a blending ratio of 65 to 95% by mass for the former and 5 to 35% by mass for the latter. Specifically, for example, one or more kinds such as an aliphatic polyester resin other than the polylactic acid resin, a plasticizer for polylactic acid resin, and a polyester-based elastomer can be used.

As the aliphatic polyester resin other than the polylactic acid resin, for example, a polymer containing an aliphatic dicarboxylic acid unit and an aliphatic diol unit as main components can be used, and specifically, for example, polybutylene succi. Nate, polybutylene adipate, polybutylene succinate, polybutylene succinate adipate, etc. can be used.

As the plasticizer for polylactic acid resin, for example, adipate ester or the like can be used. As the adipate ester, for example, a plasticizer composed of a diesterified product of adipic acid and a higher alcohol can be used. Specifically, a plasticizer for polylactic acid resin (trade name, DAIFATTY-101) made of adipate ester manufactured by Daihachi Chemical Industry Co., Ltd. can be used.

As the polyester-based elastomer, for example, a polyester-based elastomer having a high melting point (Tm) polyester portion as a hard segment and a low melting point (Tm) to low glass transition temperature (Tg) polyether or polyester portion as a soft segment is used. can do. Specifically, a polyester-based elastomer such as a trade name manufactured by Toray DuPont Co., Ltd., High Retort 4057, or the like can be used.

<Polybutylene succinate (PBS) resin>
When the sealant layer 12 is made of polybutylene succinate (PBS) resin, for example, the melt flow rate (MFR) is 1.0 to 30.0 g / 10 minutes, preferably 3.0 to 20. Polybutylene having a density in the range of about 1.20 to 1.30 g / cm ³ and a melting point in the range of 80 to 120 ° C. in the range of 0 g / 10 minutes (190 ° C., 2.16 kg). Succinate can be used.
Specifically, as the above polybutylene succinate, 1.4-butanediol and succinic acid are used as main components, and the polybutylene succinate is made of an aliphatic polyester resin obtained by direct dehydration polycondensation and is soft. A biodegradable polyester having properties similar to those of a polyolefin resin can be used.
As the other component, for example, lactic acid or the like can be used.

The thickness of the sealant layer 12 is preferably 20 μm or more and 40 μm or less from the viewpoint of being heat-sealed without gaps by heating. If the thickness of the sealant layer 12 is 20 μm or more, for example, when the packaging bag 1A (see FIG. 2) described later is produced using the laminate 10, a portion where three or more laminates overlap (for example, for example). The heat seal strength can be maintained at the portion where the back seal portion and the upper or lower seal portion overlap). Further, when the thickness of the sealant layer 12 is 40 μm or less, excellent hand-cutting property and dead hold property can be maintained.

(Embedded layer)
The thin-film deposition layer 13 is a barrier layer provided to suppress the permeation of oxygen and water vapor that permeate the laminate 10. As described above, the vapor deposition layer 13 of the present embodiment is provided on the surface of the sealant layer 12 on the paper substrate layer 11 side, and is formed of a metal or an inorganic oxide. The thin-film deposition layer in the present invention means a film formed by a vapor deposition method in a broad sense, and includes a film formed not only by a vacuum vapor deposition method but also by sputtering or the like.

Here, examples of the metal applied to the vapor deposition layer 13 include aluminum (Al), magnesium (Mg), tin (Sn), sodium (Na), titanium (Ti), lead (Pb), and zirconium (Zr). , Yttrium (Y), gold (Au), chromium (Cr) and the like can be used. In particular, for packaging, it is preferable to provide a vapor-deposited aluminum film.

Examples of the inorganic oxide applied to the vapor-deposited layer 13 include silica, which is an oxide of silicon (Si), in addition to aluminum oxide, titanium oxide, and the like, which are metal oxides of the above metals. In particular, for packaging, it is preferable to provide a vapor-deposited film of aluminum oxide.

The film thickness of the vapor-deposited layer 13 varies depending on the type of metal used and the like, but for example, it is desirable to arbitrarily select and form the film thickness within the range of 50 Å or more and 2000 Å or less, preferably 100 Å or more and 1000 Å or less. More specifically, in the case of a thin-film aluminum film, the film thickness is preferably 50 Å or more and 600 Å or less, more preferably 100 Å or more and 450 Å or less.

Examples of the method for forming the vapor deposition layer 13 include a physical vapor deposition method (PVD method) such as a vacuum vapor deposition method, a sputtering method, and an ion plating method, or a plasma chemical vapor deposition method, heat. Examples thereof include a chemical vapor deposition method, a chemical vapor deposition method such as a photochemical vapor deposition method, and a CVD method.

The thin-film deposition layer 13 can be formed, for example, by directly applying the above-mentioned metal or inorganic oxide to the sealant layer 12 by the above-mentioned vacuum vapor deposition method or the like.
When the vapor deposition layer 13 is provided directly above the sealant layer 12 as described above, the surface of the sealant layer 12 can be pretreated as necessary, specifically, corona discharge treatment and ozone treatment. , Low temperature plasma treatment using oxygen gas, nitrogen gas or the like, physical treatment such as glow discharge treatment, or chemical treatment such as oxidation treatment using chemicals or the like may be performed. When the vapor deposition layer 13 is provided directly above the sealant layer 12, a commercially available product, for example, VM-CPP (aluminum vapor deposition CPP film) manufactured by Toray Film Processing Co., Ltd. is applied as the sealant layer 12 including the vapor deposition layer 13. be able to. It is desirable that the thickness of the sealant layer 12 on which the thin-film deposition layer 13 is directly formed is 20 μm or more and 40 μm or less in total.
The sealant layer 12 provided with the thin-film deposition layer 13 is not limited to the above-mentioned form, and is, for example, an anchor layer between the sealant layer 12 and the vapor-deposited layer 13 to further strengthen the adhesion between the two layers. An intermediate layer may be further provided.

The oxygen permeability of the sealant layer 12 provided with the vapor-deposited layer 13 measured at 23 ° C. and 90% RH according to JIS K 7126-2 is, for example, 5 cc / when the above-mentioned commercially available aluminum-deposited CPP film is used. It is about m ² / day / atm or more and 20 cc / m ² / day / atm or less, and the oxygen blocking property is not sufficient. Therefore, it is necessary to improve the oxygen barrier property by combining with the barrier adhesive layer described later.

(Barrier adhesive layer)
The barrier adhesive layer 14 is a layer composed of an adhesive having a barrier property that suppresses the permeation of oxygen and water vapor, and is provided between the paper base layer 11 and the vapor deposition layer 13 to form a paper base layer. 11 and the vapor deposition layer 13 are joined. The barrier adhesive layer 14 is provided to further suppress oxygen that permeates the laminate and water vapor that cannot be suppressed by the above-mentioned vapor deposition layer 13. Specifically, a fine uneven shape is formed on the surface of the vapor-deposited layer 13, and at the fine level, the thickness of the vapor-deposited layer 13 is not uniform, and the barrier property of the relatively thin portion becomes low as a whole. Although the barrier property becomes non-uniform, when the barrier adhesive layer 14 comes into contact with the vapor deposition layer 13, the uneven shape is filled and flattened, so that the barrier property becomes uniform and oxygen and water vapor permeate. The effect of suppressing water vapor can be further enhanced.

The barrier adhesive layer 14 is a cured resin composition containing a resin (polyol) having two or more hydroxyl groups in one molecule and an isocyanate compound (polyisocyanate) having two or more isocyanate groups in one molecule. It is preferably a urethane-based adhesive having a urethane bond. The urethane adhesive is preferably a two-component curable type. As a configuration for imparting a barrier property in the resin composition, a method of introducing a skeleton having a barrier property into the resin constituting the resin composition (barrier organic adhesive), and a phosphoric acid-modified compound in the resin composition. Examples thereof include a method of containing a plate-like inorganic compound in the resin composition (barrier inorganic adhesive), and one or two or more of these can be combined.

As a method for introducing a skeleton having a barrier property into the resin constituting the resin composition, the main skeleton of the resin (polyol) is polyester or polyester polyurethane, and the ortho-oriented aromatic dicarboxylic acid or its above is used as a polyester constituent monomer component. Those containing an anhydride are preferable.

The resin has two or more hydroxyl groups in one molecule, and the main skeleton has a polyester structure or a polyester polyurethane structure. The polyester portion of the main skeleton structure is obtained by polycondensing a polyvalent carboxylic acid and a polyhydric alcohol by a known and commonly used method.
Examples of the polyvalent carboxylic acid include an aliphatic polyvalent carboxylic acid and an aromatic polyvalent carboxylic acid. Specific examples of the aliphatic polyvalent carboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecandicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid.

Specific aromatic polyvalent carboxylic acids include orthophthalic acid, terephthalic acid, isophthalic acid, pyromellitic acid, trimellitic acid, 1,2-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, and 2,3-naphthalene. Dicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid Acids and anhydrides of these dicarboxylic acids; polybasic acids such as p-hydroxybenzoic acid and p- (2-hydroxyethoxy) benzoic acid can be mentioned. As the polyvalent carboxylic acid, these can be used alone or in combination of two or more.

In the present invention, it is preferable that the polyvalent carboxylic acid contains an ortho-oriented aromatic dicarboxylic acid or an anhydride thereof as a structure having a barrier property. The ortho-oriented aromatic dicarboxylic acid or its anhydride contains 70 to 100% by mass of the ortho-oriented aromatic dicarboxylic acid or its anhydride with respect to all the polyvalent carboxylic acids of the polyester constituent monomer component. preferable.

Specific examples of the ortho-oriented aromatic dicarboxylic acid include orthophthalic acid, 1,2-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and anhydrides of these dicarboxylic acids. ..

Examples of the polyhydric alcohol include an aliphatic polyhydric alcohol and an aromatic polyhydric phenol. Specific examples of the aliphatic polyhydric alcohol include ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, cyclohexanedimethanol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, and 1, Examples thereof include 6-hexanediol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol.

Specific examples of the aromatic polyhydric phenol include hydroquinone, resorcinol, catechol, naphthalenediol, biphenol, bisphenol A, hisphenol F, tetramethylbiphenol, ethylene oxide extenders thereof, and hydrogenated alicyclic group. Etc. can be exemplified.

The isocyanate compound (polyisocyanate) has two or more isocyanate groups in the molecule and may be either aromatic or aliphatic, may be either a low molecular weight compound or a high molecular weight compound, and is a diisocyanate compound having two isocyanate groups. Or, known compounds such as three or more polyisocyanate compounds can be used. The isocyanate compound may be a blocked isocyanate compound obtained by an addition reaction using a known isocyanate blocking agent by a known and commonly used appropriate method.

Among them, a polyisocyanate compound is preferred from the viewpoint of adhesiveness and retort resistance, and a compound having an aromatic ring is preferable from the viewpoint of imparting oxygen barrier property, and an isocyanate compound containing a metaxylene skeleton is particularly preferable.

Specific examples of the isocyanate compound include tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydride diphenylmethane diisocyanate, metaxylylene diisocyanate, hydride xylylene diisocyanate, isophorone diisocyanate, and these isocyanate compounds. Trimeric and excess amounts of these isocyanate compounds, such as ethylene glycol, propylene glycol, metaxylylene alcohol, 1,3-bishydroxyethylbenzene, 1,4-bishydroxyethylbenzene, trimethylolpropane, glycerol, pentaerythritol. , Erythritol, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine, metaxylylene diisocyanate and other low molecular weight active hydrogen compounds and their alkylene oxide adducts, various polyester resins, polyether polyols, polyamide polymers Examples thereof include an adduct-form, a bullet-form, and an allophanate-form obtained by reacting with an active hydrogen compound and the like.

(Phosphate-modified compound)
The resin composition may contain a phosphoric acid-modified compound in addition to the above resin. The phosphoric acid-modified compound has an effect of improving the adhesive strength to the inorganic member, and a known and commonly used compound can be used.

Specifically, phosphoric acid, pyrophosphate, triphosphate, methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, dibutyl phosphate, 2-ethylhexyl acid phosphate, bis (2-ethylhexyl) phosphate, isododecyl acid phosphate, butoxyethyl. Acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, polyoxyethylene alkyl ether phosphoric acid and the like can be mentioned, and one or more of these can be used.

(Plate-shaped inorganic compound)
In addition to the above resins, the resin composition may contain a plate-like inorganic compound. The plate-like inorganic compound has an effect of improving the laminating strength and oxygen barrier property of the laminated body via the barrier adhesive layer 14.
Specific examples of the plate-like inorganic compound (M) include kaolinite-serpentine clay minerals (haloisite, kaolinite, enderite, deckite, nacrite, etc., antigolite, chrysotile, etc.), pyrophyllite-talc. (Pyrophyllite, talc, kaolin, etc.) and the like, and one or more of these can be used.

The thickness of the barrier adhesive layer 14 is 0.5 to 8.0 μm, preferably 1.0 to 5.0 μm, and more preferably 2.0 to 4.5 μm. If it is thinner than the above range, the gas barrier property tends to be insufficient, and if it is thicker than the above range, the bending resistance tends to be inferior, which tends to lead to a decrease in the gas barrier property after bending.

The barrier adhesive layer 14 may be composed of a solvent-based adhesive or a solvent-free (non-solvent-based) adhesive. When a solvent-based adhesive is used for the barrier adhesive layer 14, for example, PASLIM VM001 / 108CP manufactured by DIC, which is a barrier organic adhesive, can be applied, and the paper base material layer 11 and the vapor deposition layer 13 can be applied. The sealant layer 12 provided can be bonded by a dry laminating method. When a solvent-free adhesive is used for the barrier adhesive layer 14, for example, PASLIM NSRD011 / NSRD006 manufactured by DIC, which is a barrier organic adhesive, can be applied, and the paper base material layer 11 and the vapor deposition layer 13 can be applied. The sealant layer 12 provided with the above can be bonded by a non-solvent laminating method.
Further, as other barrier organic adhesives, those disclosed in JP-A-2003-300271 and JP-A-2010-012769, an adhesive containing a non-bisphenol A-based polyepoxy resin as a main agent and a polyamine as a curing agent. Therefore, "Maxive (registered trademark)" marketed by Mitsubishi Gas Chemicals Co., Ltd. as a gas barrier adhesive can also be used.

(Laminated body)
The laminate 10 of the present embodiment has the barrier adhesive layer 14 having the above-mentioned barrier property and the sealant layer 12 provided with the vapor deposition layer 13, so that oxygen and water vapor that permeate the laminate 10 and water vapor. Can be significantly suppressed.
From the viewpoint of more effectively ensuring the barrier property of oxygen, the laminated body 10 as a whole has an oxygen permeability of 3.0 cc / m measured at 23 ° C. and 90% RH in accordance with JIS K 7126-2. ^{It is desirable that it is 2} / day / atm or less.
Further, from the viewpoint of more effectively ensuring the barrier property of water vapor, the laminated body 10 has a water vapor permeability measured in accordance with the JIS K 7129 B method under the measurement conditions of 40 ° C. and 90% RH. However, when an unstretched polypropylene resin film is used for the sealant layer 12, ^{it is preferably 2.0 g / m 2} / day / atm or less, and when a polyethylene resin film is used for the sealant layer, 5.0 g / m ² It is desirable that it is less than / day / atm.

In the laminated body 10 of the present embodiment, the mass (basis weight) per ^{1 m 2} of the paper base material layer 11 is t1 from the viewpoint of ensuring excellent hand-cutting property and dead hold property as a whole laminated body, and the vapor deposition layer 13 It is desirable that the relationship of the following formula (1) is satisfied when the mass (basis weight) per ^{1 m 2 of the} sealant layer 12 provided with the above is t2. Here, t2 indicates the basis weight of the sealant layer 12 and the vapor deposition layer 13 when the vapor deposition layer 13 is provided directly above the sealant layer 12, and an anchor layer or the like is provided between the sealant layer 12 and the vapor deposition layer 13. If the intermediate layer is present, it indicates the total basis weight of the sealant layer 12, the vapor-deposited layer 13, and the intermediate layer.

Equation (1) 1.0 ≤ t1 / t2 ≤ 5.0

If t1 / t2 is less than 1.0, the ratio of the sealant layer 12 including the vapor-deposited layer 13 to the paper base material layer 11 in the laminated body 10 becomes too large, and the dead hold property of the laminated body 10 deteriorates. It is not desirable because it will do. Further, when t1 / t2 is larger than 5.0, the ratio of the sealant layer 12 including the vapor-deposited layer 13 to the paper base material layer 11 in the laminated body 10 becomes too small, and the hand-cutting property of the laminated body 10 is lowered. This is not desirable because the sealant layer 12 becomes too thin and sufficient heat sealing performance cannot be obtained.
If the thickness of the sealant layer 12 is 20 μm or more as described above, sufficient heat sealability can be obtained.

Further, in order to secure better hand-cutting property and dead-holding property, the paper base material layer 11 of the laminated body 10 has a basis weight of 30 g / m ² or more and 100 g / m ² or less as described above. It is preferably 35 g / m ² or more and 70 g / m ² or less.
If the basis weight of the paper base material layer 11 is ^{larger than 100 g / m 2} , the paper base material layer becomes too thick and the hand-cutting property of the laminated body is lowered, which is not desirable. Further, when the basis weight of the paper base material layer 11 ^{is less than 30 g / m 2} , the paper base material layer becomes too thin and the dead hold property of the laminated body is lowered, which is not desirable.

(Packaging body using laminated body)
FIG. 2 is a diagram showing a package using the laminated body of the present embodiment. FIG. 2A is a diagram showing a packaging bag 1A which is an example of a package using the laminate 10 of the present embodiment, and FIG. 2B is a package using the laminate 10 of the present embodiment. It is a figure which shows the packaging bag 1B which is another example of a body.
FIG. 3 is a diagram showing another example of a package using the laminated body of the present embodiment. FIG. 3A is a plan view showing a packaging bag 1C which is an example of a packaging body using the laminated body 10 of the present embodiment, and FIG. 3B is a sectional view taken along line B of FIG. 3A. Is.
FIG. 4 is a diagram showing another example of a package using the laminated body of the present embodiment. FIG. 4 (A) is a plan view showing a packaging bag 1D which is an example of a package using the laminated body 10 of the present embodiment, and FIG. 4 (B) is a sectional view taken along line B of FIG. 4 (A). Is.
FIG. 5 is a diagram showing another example of a package using the laminated body of the present embodiment. 5 (A) is a diagram showing a packaging bag 1E which is an example of a package using the laminated body 10 of the present embodiment, and FIG. 5 (B) is a sectional view taken along line B of FIG. 5 (A). Yes, FIG. 5C is a diagram illustrating a usage pattern of the packaging bag 1E.
FIG. 6 is a diagram showing another example of a package using the laminated body of the present embodiment. FIG. 6A is a diagram showing a box-shaped package 1F which is an example of a package using the laminate 10 of the present embodiment, and FIG. 6B is a diagram showing the laminate 10 of the present embodiment. It is a figure which shows the box type package body 1G which is another example of the package body used.

The laminate 10 of the present embodiment can be applied to, for example, the pillow-type packaging bag 1A shown in FIG. 2A and the flat pouch-type packaging bag 1B shown in FIG. 2B. The pillow-shaped packaging bag 1A shown in FIG. 2A is a cylinder formed by heat-sealing the sealant layers 12 on the pair of opposite sides of one rectangular laminate 10 to form the back seal portion 2. It is manufactured by heat-sealing the upper and lower tubular openings, respectively, to form the upper seal portion 3 and the lower seal portion 4.
Further, in the packaging bag 1B shown in FIG. 2B, one rectangular laminated body 10 is folded in half so that the sealant layer 12 faces each other, and the three sides other than the fold line 5 are heat-sealed to seal. It is produced by forming the part 6.

Further, the packaging bag 1C shown in FIG. 3 is a packaging bag in which an opening / closing portion by a zipper is provided at an opening portion of the flat pouch type packaging bag shown in FIG. 2 (B). Specifically, as shown in FIG. 3A, a chuck portion 24 is provided inside the vicinity of the upper seal portion 21 of the packaging bag 1C along the upper seal portion 21. As shown in FIG. 3B, the chuck portion 24 is composed of, for example, a male member 24A that can be fitted to each other and a female member 24B, and is male on the inner surface of the laminate on the front surface side of the packaging bag 1C. The female member 24B is arranged on the inner surface of the laminated body on the back surface side of the member 24A facing each other, and the female member 24B is fitted to each other, so that the chuck portion 24 is closed.
Further, between the upper seal portion 21 and the chuck portion 24, a notch portion 25 for opening is provided by cutting out a part of the side seal portions 22 and 23 at both ends of the packaging bag 1C. With this configuration, the packaging bag 1C can be opened and closed by the chuck portion 24 after the upper seal portion 21 is separated from the main body of the packaging bag 1C by the notch portion 25 and opened.

As shown in FIG. 4, the laminate of the present embodiment can also be used for the stand pouch type packaging bag 1D. In the packaging bag 1D shown in FIG. 4, two rectangular laminated bodies 10A and 10B are stacked so that the sealant layers 12 face each other, and the upper side and both side surfaces are heat-sealed. Further, on the lower side, the laminated body 10C folded in half is sandwiched between the two laminated bodies 10A and 10B so that the sealant layer 12 faces each other, and the outer peripheral edge of the laminated body 10C and the laminated body 10A, It is formed by heat-sealing with 10B. With such a form, the packaging bag 1D filled with the contents becomes a pouch that can stand on its own with the laminated body 10C as the bottom surface, that is, a so-called standing pouch.
Similar to the packaging bag 1C shown in FIG. 3 above, the chuck portion 24 is provided along the upper seal portion 21, and the side seal portions 22 and 23 between the chuck portion 24 and the upper seal portion 21 are provided. A notch portion 25 may be provided in a part thereof so that the opening can be opened and closed after the packaging bag is opened.

Further, as shown in FIG. 5, the laminate 10 of the present embodiment can also be applied to the packaging bag 1E provided with the intermediate seal portion 31. As shown in FIGS. 5 (A) and 5 (B), the packaging bag 1E is formed by folding the long laminated body 10A in half so that the front side and the back side have different lengths, and the short side (the short side ( The upper end edge of the surface side) and the lower end edge of the rectangular laminated body 10B are joined by heat sealing to form an intermediate sealing portion 31. Further, the upper end edge of the long side (back surface side) and the upper end edge of the rectangular laminated body 10B are joined by heat sealing to form the upper sealing portion 32, and both side edges of the joined laminated bodies 10A and 10B are heat-sealed. It is formed by joining to form side seal portions 33 and 34.

In the packaging bag 1E, a notch portion 35 for opening is formed in a part of the side seal portions 33 and 34 between the upper seal portion 32 and the intermediate seal portion 31, and the upper seal is triggered by this notch portion 35. The packaging bag 1E can be opened by separating the portion 32 from the main body of the packaging bag. In the opened packaging bag 1E, as shown in FIG. 5C, the portion above the intermediate seal portion 31 of the packaging bag 1E is set to the lower portion so that the intermediate seal portion 31 is located at the upper end. The opening can be closed by folding them so that they overlap. As described above, the laminate used for the packaging bag 1E has a paper base material layer, so that it has excellent dead-holding properties, can be appropriately maintained in a bent state, and is the contents of the packaging bag. It is possible to prevent objects from leaking from the opening or coming into contact with the outside air as much as possible.
If necessary, the packaging bag 1E may be formed in a self-supporting standing type by providing a laminate forming a bottom portion as in the above-mentioned packaging bag 1D (see FIG. 4).

As shown in FIG. 6, the laminated body 10 of the present embodiment can also be applied to the box-shaped package 1F. The package 1F shown in FIG. 6A is a box-shaped package composed of five laminated bodies 10, and the laminated body 10A forming the bottom portion and the laminated body forming the front surface portion and the back surface portion, respectively. It is formed of 10B and 10C and the laminated bodies 10D and 10E forming the side portions. In each laminated body, a box-shaped package 1F is formed by joining the edges of adjacent laminated bodies by heat sealing so that the sealant layer 12 is inside the package 1F.
Further, in the package 1F shown in FIG. 6A, the upper portion, the upper side edge of the laminate 10B forming the front portion, and the laminate 10C forming the back portion are directly heat-sealed, and the upper portion is formed. The seal portion 41 and the side seal portions 42, 43 are formed so that the upper side is tapered as compared with the bottom side.
In the package 1F, a chuck portion 44 that can be opened and closed along the upper seal portion 41 and a notch portion 45 for opening the package 1F are located between the chuck portion 44 and the upper seal portion 41. It is provided on a part of the side seal portions 42 and 43 of the above. As a result, after the upper seal portion 41 is separated from the main body of the package 1F by the notch portion 45 and opened, the upper seal portion 41 can be opened and closed by the chuck portion 44.
The box-shaped package 1F is not limited to the example of FIG. 6 (A), and may be formed in a three-dimensional shape such as a rectangular parallelepiped or a cube as shown in FIG. 6 (B). ..

As described above, the laminate 10 of the present embodiment is excellent in hand-cutting property and dead-holding property as compared with the conventional packaging material. Therefore, by using the laminate 10 in such a packaging bag, the packaging bag can be opened. The part can be cut by hand and easily opened. In addition, the opened opening can be bent and closed to maintain the closed state.
The form of the packaging bag is not limited to the pillow type and the flat pouch (three-way pouch) type described above, and may be a gusset type packaging bag.
Further, the laminated body 10 of the present embodiment can be used as a lid member for closing the opening of the container as another example of the package, and further, not only the lid member but also the three-dimensional container itself is laminated. It may be formed by. As described above, the laminated body 10 of the present embodiment has excellent dead-holding property, so that the three-dimensional shape of the container or the like can be maintained.
The "packaging body" in the present invention is a general term when the laminate of the present invention is used as a packaging material, and includes not only packaging bags but also those having a container shape, such as a lid material. Even the members that form a part of the packaging container are within the scope of the "packaging body".

Hereinafter, the present invention will be described in more detail based on Examples.
[Example 1]
The laminate of Example 1 uses coated paper 55 g / m ² (manufactured by Ryuou Coat Daio Paper Corporation) as the paper base material layer, and Sias HR (DIC Graphics Co., Ltd.), which is a gravure ink on the non-coated surface of the coated paper. A pattern layer was formed by performing gravure printing with a dry thickness of 1 μm. Next, KS-10 (manufactured by DIC Graphics Corporation) was applied as an OP (overprint) varnish on the gravure print (picture layer) to a dry thickness of 1 μm to form a surface layer.
Next, a non-solvent barrier adhesive (PASLIM NSRD011 / NSRD006 DIC Corporation) is applied to the non-printing surface (coated surface) of the paper substrate layer so as to have a dry thickness of 3 μm to form a barrier adhesive layer. did. After that, the aluminum-deposited CPP film 25 μm (VM-CPP 2703 manufactured by Toray Film Processing Co., Ltd.), which is a sealant layer having a vapor-deposited layer, is bonded to the vapor-deposited surface by a non-solvent laminating method and aged at 40 ° C. for 3 days. The laminated body of Example 1 was obtained.

[Example 2]
The laminate of Example 2 is the laminate of Example 1 except that the paper substrate layer is coated paper 37 g / m ² (coated oil-resistant paper manufactured by Daio Paper Corporation) and the thickness of the aluminum-deposited CPP film is changed to 40 μm. Similar to the body.

[Example 3]
In the laminate of Example 3, printing was performed on the coated layer side of the coated paper, which is a paper base material layer, to form a pattern layer, and a non-solvent barrier adhesive (PASLIM NSRD011 / NSRD006 DIC Corporation) was applied to the non-coated surface. It is the same as the laminated body of Example 1 except that it is coated with (manufactured).

[Example 4]
The laminate of Example 4 is a sealant layer provided with a thin-film deposition layer after the adhesive is applied and dried with a solvent-based barrier adhesive (PASLIM VM001 / 108CP DIC) to a dry thickness of 4 μm. It is the same as the laminate of Example 1 except that the vapor-deposited surface of the aluminum-deposited CPP film 25 μm (VM-CPP 2703 manufactured by Toray Film Processing Co., Ltd.) is bonded by the dry laminating method.

[Example 5]
In the laminate of Example 5, printing was performed on the coated layer side of the coated paper, which is a paper base material layer, to form a pattern layer, and a solvent-based barrier adhesive (PASLIM VM001 / 108CP DIC Corporation) was used on the non-coated surface. ) Is applied, which is the same as that of the laminated body of Example 4.

[Example 6]
The laminate of Example 6 uses coated paper 55 g / m ² (manufactured by Ryuou Coat Daio Paper Corporation) as the paper base material layer, and Sias HR (manufactured by DIC Graphics Corporation) which is a gravure ink on the coated surface of the coated paper. ) Was used to perform gravure printing with a dry thickness of 1 μm to form a pattern layer. Next, KS-10 (manufactured by DIC Graphics Corporation) was applied as an OP (overprint) varnish on the gravure print (picture layer) to a dry thickness of 1 μm to form a surface layer.
Next, a solvent-based barrier adhesive (PASLIM VM001 / 108CP DIC) was dried on the vapor-deposited surface of an aluminum-deposited CPP film 25 μm (VM-CPP 2703 manufactured by Toray Film Processing Co., Ltd.) as a sealant layer provided with a vapor-deposited layer. After coating and drying to a size of 4 μm, the non-printed surface of coated paper was bonded by a dry laminating method and aged at 40 ° C. for 3 days to obtain a laminate of Example 6.

[Example 7]
The laminate of Example 7 is the same as the laminate of Example 1 except ^{that the basis weight of the paper substrate layer is changed to 98 g / m 2.}

[Example 8]
The laminate of Example 8 is the same as the laminate of Example 1 except that the ^{paper base material layer is changed to 66 g / m 2 of barrier coated paper (Nippon Paper Industries Shield Plus).}

[Comparative Example 1]
In the laminate of Comparative Example 1, the paper base material layer ^{was changed to 34 g / m 2 of} coated paper (manufactured by Daio Paper Corporation, an oil-resistant coated paper), and the thickness of the aluminum-deposited CPP film (sealant layer including the vapor-deposited layer) was changed. Is the same as that of the laminated body of Example 1 except that is changed to 40 μm.

[Comparative Example 2]
The laminate of Comparative Example 2 is the same as the laminate of Example 1 except ^{that the basis weight of the paper base material layer is changed to 120 g / m 2.}

[Comparative Example 3]
The laminate of Comparative Example 3 was the same as the laminate of Example 1 except that the non-solvent barrier adhesive was changed to a general-purpose non-solvent ester adhesive (manufactured by A-695 / A-95 Mitsui Chemicals, Inc.). The same is true.

[Comparative Example 4]
The laminate of Comparative Example 4 is the same as the laminate of Example 4 except that the barrier adhesive is changed to a general-purpose solvent-based ester adhesive (A-315 / A-50 manufactured by Mitsui Chemicals, Inc.).

The evaluation results of each laminated body of Examples and Comparative Examples are summarized in Table 1 below.

[Evaluation of barrier property]
When the oxygen permeability of the prepared laminates of Examples and Comparative Examples was measured at 23 ° C. and 90% RH in accordance with JIS K 7126-2, as shown in Table 1, a general-purpose adhesive that is not a barrier adhesive was used. The laminates of Comparative Example 3 and Comparative Example 4 using the non-solvent adhesive and the general-purpose solvent-based adhesive of the above have significantly more oxygen than the laminates of the other Examples, Comparative Example 1 and Comparative Example 2. It was confirmed that the amount of transmission was large. As a result, it was confirmed that the laminated body of each example had significantly improved oxygen permeability due to the barrier adhesive layer. An oxygen permeability measuring device (manufactured by Mocon, product name "OXTRAN") was used.

Further, when the water vapor permeability of the laminates of Examples and Comparative Examples was measured at 40 ° C. and 90% RH in accordance with the JIS K 7129B method, a barrier adhesive layer was provided as in the case of oxygen. It was confirmed that the laminated bodies of Comparative Example 3 and Comparative Example 4 did not have a significantly larger amount of water vapor permeation than the laminated bodies of other Examples, Comparative Example 1 and Comparative Example 2. From this, it was confirmed that the water vapor permeability of the laminated body of each example was remarkably improved by the barrier adhesive layer. A water vapor transmittance measuring device (manufactured by Mocon Co., Ltd., product name "Permatlan") was used.

[Evaluation of hand cutting]
The evaluation of hand-cutting property is a sensitivity evaluation in which an experimenter determines whether or not the laminated body of each of the prepared Examples and Comparative Examples can be cut properly by hand. The case where it was cut was marked with "◎", the case where it was cut along the planned line to some extent was marked with "○", and the case where it was not cut or cut in an unplanned direction was marked with "x".

As shown in Table 1, in the laminate of Comparative Example 2, the ratio (t1 / t2) of the basis weight t1 of the paper base material layer to the basis weight t2 of the sealant layer including the vapor deposition layer is 5.33. Since the basis weight t1 of the paper base material layer was too large compared to the basis weight t2 of the sealant layer provided with the vapor deposition layer, the evaluation of the hand-cutting property was “x”.
On the other hand, in the laminated body of each example, the evaluation of the hand-cutting property was "○" or "◎", and each t1 / t2 was in a preferable range (1.00 or more and 5.00 or less). Confirmed to meet. It was also confirmed that in the laminated body of each example, the basis weight of each paper base material layer ^{satisfied the preferable range (30 g / m 2} or more and 100 g / m ^{2 or less).}

[Evaluation of dead hold]
In the evaluation of the dead hold property, the laminated body of each of the prepared Examples and Comparative Examples is folded in half, allowed to stand for 5 minutes, and then the experimenter determines whether or not the shape at the time of folding is maintained. It is a sensitivity evaluation, and in Table 1, after folding in half, the case where the shape when folded is maintained even in the stationary state is marked with "◎", and the folded form in the stationary state is before folding slightly. However, if the shape of the two folds can be almost maintained, it will be marked as "○", and even if it is folded, it will return to its original shape, or some creases will remain, but it will return to the shape before it was folded. The case was set to "x".

As shown in Table 1, in the laminate of Comparative Example 1, the ratio (t1 / t2) of the basis weight t1 of the paper base material layer to the basis weight t2 of the sealant layer including the vapor deposition layer is 0.94. It is probable that the evaluation of the dead hold property was "x" because the basis weight t1 of the paper base material layer was too small as compared with the basis weight t2 of the sealant layer provided with the vapor deposition layer.
On the other hand, in each of the laminated bodies of each example, the evaluation of the dead hold property was "○" or "◎", and each t1 / t2 was in a preferable range (1.00 or more and 5.00 or less). Confirmed to meet.

1 (1A, 1B, 1C, 1D, 1E, 1F, 1G) Packaging bag (packaging body)
10 Laminated body 11 Paper base material layer 12 Sealant layer 13 Deposited layer 14 Barrier adhesive layer

Claims (7)

Paper substrate layer and
A sealant layer provided on one surface side of the paper base material layer and provided with a metal or inorganic oxide vapor deposition layer, and a sealant layer.
It is provided between the paper base material layer and the vapor deposition layer, and includes a barrier adhesive layer for joining the paper base material layer and the vapor deposition layer.
The oxygen permeability measured at 23 ° C. and 90% RH according to JIS K 7126-2 is 3.0 cc / m ² / day / atm or less.
Let t1 be the mass per ^{1 m 2 of the} paper base material layer.
When the mass per ^{1 m 2 of the} sealant layer provided with the vapor-deposited layer is t2,
A laminate that satisfies 1.0 ≦ t1 / t2 ≦ 5.0. The laminate according to claim 1, wherein the paper substrate layer has a basis weight of 30 g / m ² or more and 100 g / m ^{2 or less.} The laminate according to claim 1 or 2, wherein the sealant layer has a thickness of 20 μm or more. The laminate according to any one of claims 1 to 3, wherein the sealant layer is an unstretched polyolefin resin film. The unstretched polyolefin resin film is an unstretched polypropylene resin film.
The laminate according to claim 4, wherein the unstretched polypropylene resin film contains biomass polyethylene. The barrier adhesive layer is a cured product of a resin composition containing a resin having two or more hydroxyl groups in one molecule and an isocyanate compound having two or more isocyanate groups in one molecule.
The laminate according to any one of claims 1 to 5, wherein the main skeleton of the resin is polyester or polyester polyurethane, and the polyester constituent monomer component contains an ortho-oriented aromatic dicarboxylic acid or an anhydride thereof. A package body formed by using the laminate according to any one of claims 1 to 6.

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