JP2013248743A - Packaging material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a packaging material excellent in nonadsorptivity and having good light shielding properties, gas barrier properties and heat sealability.SOLUTION: A packaging material has at the least: a first base material layer 1 having a transparent barrier layer b and a synthetic resin layer a; a second base material layer 2 having a metallic barrier layer c and another synthetic resin layer d; and a sealant layer 3; wherein the sealant layer 3 has a straight-chain low density polyethylene resin layer e or an ethylene-methacrylic acid copolymer resin layer e and a cyclic polyolefin resin layer f.

Description

  The present invention relates to a non-adsorbing packaging material in which the adsorption amount of active ingredients contained in contents such as pharmaceuticals, cosmetics, and foods is reduced, and more specifically, the adsorption amount of the contents can be reduced. In addition, the present invention relates to a packaging material having excellent light shielding properties, gas barrier properties, and heat sealing properties.

  Conventionally, the innermost layer of a packaging material such as a packaging bag or a lid is made of a polyolefin resin such as polyethylene or polypropylene having excellent heat sealability, or a copolymer resin such as ionomer or ethylene / methacrylic acid copolymer resin (EMAA). It is used. These resins can achieve high adhesion strength by heat sealing, but are known to easily adsorb various organic compounds. Therefore, the packaging material having these resins as the innermost layer, that is, the layer in contact with the contents, is not suitable for packaging of pharmaceuticals, cosmetics, foods, etc. containing organic compounds as active ingredients, and the active ingredients are previously contained in the contents. It is necessary to take measures such as adding more. Further, since the above resin is inferior in light shielding property and gas barrier property, when forming a packaging material using the above resin, for example, it is necessary to provide an aluminum foil or the like as a barrier layer. Peeling (delamination) occurs between adjacent layers, and it cannot withstand practical use.

  For this reason, as materials used for the sealant layer, materials that have a heat sealing property and are difficult to adsorb active ingredients have been developed. Typically, a packaging material having a non-adsorptive sealant layer made of acrylonitrile resin as the innermost layer is used (Patent Document 1). However, since acrylonitrile-based resin has poor heat sealability and is expensive, development of a more preferable non-adsorptive sealant is required.

  On the other hand, for example, Patent Document 2 discloses a non-adsorptive packaging material in which the innermost layer is formed of an aluminum foil or an inorganic vapor deposition film. The packaging material is used by making a bag by partially forming an adhesive resin layer on the aluminum foil or vapor deposition film. As the adhesive resin layer, urethane resin, vinyl chloride-vinyl acetate copolymer, acrylic resin and the like are disclosed. However, such a packaging material has a complicated manufacturing process.

JP-A-7-132946 Japanese Patent Laid-Open No. 10-45176

  The present invention solves the above problems and provides a packaging material that makes it difficult to adsorb organic compound components, that is, has excellent non-adsorption properties, and has good light shielding properties, gas barrier properties, and heat seal properties. With the goal.

As a result of various studies, the inventor has at least a first base material layer having a transparent barrier layer and a synthetic resin layer, a second base material layer having a metal barrier layer and a synthetic resin layer, and a package having a sealant layer. The first base material layer and the second base material layer are laminated so that the transparent barrier layer and the metal barrier layer face each other, and the sealant layer is a linear low density A polyethylene resin (LLDPE, density 0.900-0.940 g / cm ³ ) layer or ethylene / methacrylic acid copolymer resin (EMAA) layer, and a cyclic polyolefin-based resin layer; The linear low-density polyethylene resin layer or ethylene / methacrylic acid copolymer resin layer in the sealant layer and the synthetic resin layer in the first or second substrate layer are opposed to the first or second substrate layer. It is characterized by being laminated to To, the packaging material were found to achieve the above object.

The present invention is characterized by the following points.
1. A packaging material having at least a first base material layer having a transparent barrier layer and a synthetic resin layer, a second base material layer having a metal barrier layer and a synthetic resin layer, and a sealant layer,
The first base material layer and the second base material layer are laminated so that the transparent barrier layer and the metal barrier layer face each other.
The sealant layer has a linear low density polyethylene resin layer or an ethylene / methacrylic acid copolymer resin layer, and a cyclic polyolefin resin layer, and
The sealant layer and the first or second base material layer include a linear low density polyethylene resin layer or an ethylene / methacrylic acid copolymer resin layer in the sealant layer and the first or second base material layer. The packaging material, wherein the synthetic resin layers are laminated so as to face each other.
2. The sealant layer is composed of two layers of a linear low density polyethylene resin layer and a cyclic polyolefin resin layer, and the linear low density polyethylene resin layer is a first or second group via an anchor coat layer. 2. The packaging material according to 1 above, wherein the packaging material is laminated on a synthetic resin layer in the material layer.
3. The anchor coat layer is an aqueous dispersion in which a polyolefin copolymer resin containing 0.01 to 5% by mass of an unsaturated carboxylic acid or an anhydride thereof is dispersed so that the number average particle diameter thereof is 1 μm or less, and An aqueous dispersion formed so as not to substantially contain a nonvolatile aqueous solubilizing aid in the aqueous dispersion is applied to the surface of the synthetic resin layer of the first base material layer or the second base material layer at the time of drying. 3. The packaging material according to 2 above, wherein the packaging material is formed by coating, heating and drying so as to have a thickness of 0.1 to 2 μm.
4). 3. The packaging material according to 2 above, wherein the anchor coat layer is a layer formed by curing a composition mainly composed of an epoxy resin composition comprising an epoxy resin and an epoxy resin curing agent.
5. 2. The packaging material according to 1 above, wherein the sealant layer is a layer composed of two layers of an ethylene / methacrylic acid copolymer resin layer and a cyclic polyolefin resin layer.
6). 6. The packaging material according to any one of 1 to 5, wherein the transparent barrier layer is formed from an inorganic oxide selected from the group consisting of silicon oxide, magnesium oxide, and aluminum oxide.
7). The packaging material according to any one of the above 1 to 6, wherein the metal barrier layer is formed of a metal or alloy selected from the group consisting of aluminum, copper, zinc, gold and silver and alloys thereof.
8). The packaging material according to any one of the above 1 to 7, wherein the linear low-density polyethylene resin layer and the cyclic polyolefin-based resin composition layer are laminated by coextrusion coating.

  The sealant layer for a packaging material containing the cyclic polyolefin resin composition of the present invention hardly adsorbs various organic compounds, for example, medicinal components such as l-menthol and methyl salicylate. In addition, as described above, the cyclic polyolefin resin contained as a main component exhibits a high intermolecular force, and thus has a dense surface structure with a close intermolecular distance. Therefore, since elution of a low molecular weight component can be suppressed, it is excellent in aroma retention property, and shows sufficient heat sealability to form the innermost layer of the packaging material.

In general, it is known that a cyclic polyolefin-based resin has a high intermolecular force during melt film formation and causes aggregation between polymers. As a result, it is difficult to obtain a uniform film surface by agglomerating the resin throughout the film to form a knob-like gel mass. This tendency becomes more prominent at the time of film formation by the inflation method, and the cyclic polyolefin resin film obtained by the method generates innumerable gel lumps on the entire surface.

  However, according to the present invention, by forming the cyclic polyolefin resin layer adjacent to the LLDPE layer or the EMAA layer together, non-uniform aggregation of the molecules of the cyclic polyolefin resin is suppressed. Therefore, the sealant layer of the packaging material of the present invention is easy to form a film, and can form a beautiful layer that is homogeneous and has good transparency. In addition, the generation of gel lumps can be suppressed during high-speed film formation by the inflation method.

  In such a packaging material of the present invention, the cyclic polyolefin resin layer has a close surface structure with a close intermolecular distance based on the high intermolecular force of the cyclic polyolefin resin, and the LLDPE layer or The EMAA layer exhibits high interlayer adhesion with the cyclic polyolefin resin layer, and imparts good film forming stability to the cyclic polyolefin resin layer. The packaging material of the present invention having such a structure hardly adsorbs the components in the contents, that is, has excellent non-adsorption properties.

  In addition, the sealant layer forming the packaging material of the present invention exhibits good heat sealing properties, can be heat sealed in a wide sealing temperature range, and exhibits sufficient sealing strength even at low temperature heat sealing. Therefore, processing is easy and there is little generation | occurrence | production of resin oxidation odor etc. And the packaging bag and packaging container obtained by bag-making this packaging material so that a cyclic polyolefin-type resin composition layer may become an innermost layer show favorable impact resistance.

Moreover, the packaging material of this invention has the 1st base material layer which has a transparent barrier layer, and the 2nd base material layer which has a metal barrier layer. Here, the transparent barrier layer has a gas barrier property, particularly an oxygen gas barrier property, and the metal barrier layer has both a light shielding property and a gas barrier property, particularly a water vapor gas barrier property. From light, oxygen gas, water vapor gas, or the like can be prevented, and contents can be effectively prevented from being denatured due to light or gas.
Therefore, the packaging material of the present invention is particularly suitable for forming a packaging container that is required to maintain the quality of contents.

It is a schematic sectional drawing which shows the example about the layer structure of the laminated body for packaging materials which has the sealant layer for packaging materials of this invention.

The above-described present invention will be described in more detail below.
<1> Layer Configuration of Laminate Forming Packaging Material of the Present Invention FIG. 1 is a schematic sectional view showing an example of the layer configuration of the packaging material of the present invention.
As shown in FIG. 1, the packaging material of the present invention basically has a configuration in which a first base material layer 1, a second base material layer 2, and a sealant layer 3 are laminated in this order. Here, in FIG. 1, the 1st base material layer 1 consists of two layers, a synthetic resin layer (a) and a transparent barrier layer (b), and the 2nd base material layer 2 is a synthetic resin layer (d). And the metal barrier layer (c), and the transparent barrier layer (b) and the metal barrier layer (c) are adjacent to each other. The sealant layer 3 is a layer composed of two layers, an LLDPE layer or EMAA layer (e) and a cyclic polyolefin-based resin layer (f), and the LLDPE layer or EMAA layer (e) is the second base material layer 2. Adjacent to the synthetic resin layer (d).

Said example is an example of the packaging material of this invention, and this invention is not limited to this.
For example, although not shown, when an LLDPE layer is used as a layer constituting the sealant layer in the packaging material of the present invention, an anchor coat is provided between the LLDPE layer and the synthetic resin layer of the second base material layer. A layer may be provided. The sealant layer may be provided on the first base material layer side, and in this case, the LLDPE layer or the EMAA layer is laminated so as to face the synthetic resin layer of the first base material layer.
Hereinafter, the resin names used in the present invention are those commonly used in the industry. In the present invention, the density was measured according to JIS K7112.

<2> 1st base material layer (1) Synthetic resin layer As a synthetic resin layer which comprises a 1st base material layer, polyester biaxially stretched films, such as polyethylene terephthalate and polyethylene naphthalate, nylon 6, nylon 66 A plastic film such as a biaxially stretched film of polyamide such as MXD6 (polymetaxylylene adipamide) or a biaxially stretched polypropylene film can be suitably used. These may be used singly or may be used by combining a plurality.
In the present invention, the layer thickness of the synthetic resin layer is preferably 6 to 100 μm, more preferably 9 to 50 μm.
Moreover, you may provide a printing layer further on a synthetic resin layer, and in this case, in order to improve the adhesiveness of the printing ink used for a printing layer, surface treatment (for example, corona treatment etc.) is carried out on the surface of a synthetic resin layer. ) Is preferable.

(2) Transparent barrier layer The transparent barrier layer constituting the first base material layer prevents odor leakage of the contents to the outside and intrusion of gas (especially oxygen gas) from the outside to prevent the contents from being altered. Is for.
The transparent barrier layer may be a vapor-deposited layer of an inorganic oxide such as silica, alumina, zinc oxide, magnesium oxide, indium tin oxide, ethylene-vinyl alcohol copolymer, polyamide resin, polyvinylidene chloride. It may be a barrier film layer made of at least one of a resin based on polyacrylic acid or a polyacrylonitrile based resin.
As a method for laminating the transparent barrier layer, when the transparent barrier layer is a vapor deposition layer, the layer is laminated on the synthetic resin layer by an arbitrary vapor deposition method such as a chemical vapor deposition method and a physical vapor deposition method. The layer thickness of the vapor deposition layer can be appropriately set, but is preferably in the range of about 5 to 100 nm.

Moreover, when a transparent barrier layer is a plastic film, it laminates | stacks on a synthetic resin layer through an adhesive bond layer. Any adhesive can be used for bonding, but when bonding by an extrusion lamination method (so-called sandwich lamination method), a polyolefin-based heat-adhesive resin such as ethylene-methacrylic acid is used. A copolymer, an ethylene-acrylic acid copolymer, an ionomer, a low density polyethylene resin (LDPE, density 0.910 to 0.925 g / cm ³ ) or the like is used alone, or an adhesive such as a hard resin. A resin blended with an improver can be used. Furthermore, a dry laminating method may be used. In that case, as the adhesive, for example, a two-component curable polyurethane adhesive for dry laminating can be used. The thickness of these barrier films preferably used is about 5 to 30 μm.

<3> 2nd base material layer As a synthetic resin layer used for a 2nd base material layer, the material similar to what was used for the 1st base material layer can be used. Moreover, the point which may provide a printing layer on a synthetic resin layer is also the same.
Further, the metal barrier layer constituting the second base material layer is for suppressing the penetration of light and gas (especially water vapor gas) from the outside and preventing the contents from being altered.
The metal barrier layer may be, for example, a metal foil layer made of one material selected from the group consisting of aluminum, copper, zinc, gold and silver and alloys thereof, or a vapor deposition layer thereof. May be.

As a method for laminating the metal barrier layer, when the metal barrier layer is a vapor deposition layer, any vapor deposition such as a chemical vapor deposition method and a physical vapor deposition method is performed as described in the first base material layer. It can be laminated by the method. The layer thickness of the vapor deposition layer can be appropriately set, but is preferably in the range of about 5 to 100 nm.
When the metal barrier layer is a metal foil, it can be laminated by an extrusion laminating method, a dry laminating method, or the like as described in the first base material layer. The thickness of these metal foils preferably used is about 5 to 30 μm.

<4> Sealant layer The sealant layer of the present invention has an LLDPE layer or an EMAA layer and a cyclic polyolefin resin layer. In the packaging material of the present invention, the LLDPE layer or the EMAA layer is positioned on the surface (bonding surface) of the sealant layer and is laminated so as to face the synthetic resin layer of the first or second base material layer.
(1) Structure of sealant layer In one embodiment of the present invention, the sealant layer is a layer composed of two layers of an LLDPE layer or an EMAA layer and a cyclic polyolefin-based resin layer. In the sealant layer having this configuration, the cyclic polyolefin-based resin layer is the outermost layer of the packaging material of the present invention, that is, the innermost layer of the packaging container, and therefore can exhibit excellent non-adsorbability.
In this configuration, the total thickness of the sealant layer may be arbitrary, but preferably has a layer thickness of 12 to 150 μm from the viewpoint of stable film formation and product cost. Here, the thickness of the cyclic polyolefin-based resin composition layer and the LLDPE layer or EMAA layer can be appropriately set according to the use of the packaging material, but stable film formation, non-adsorption and product cost From the viewpoint, the layer thickness of the cyclic polyolefin-based resin composition layer is desirably 2 to 30 μm, and the layer thickness of the LLDPE layer or the EMAA layer is desirably 10 to 120 μm.

(2) Linear low-density polyethylene resin (LLDPE) layer or ethylene / methacrylic acid copolymer resin (EMAA) layer In the present invention, the LLDPE constituting the LLDPE layer in the sealant layer has a density of 0.900 to 0.00. 940 g / cm ³ linear polyethylene, using a single-site catalyst such as a metallocene catalyst or a multi-site catalyst such as a Ziegler-Natta catalyst, ethylene and an α-olefin having 3 to 20 carbon atoms at low temperature, It is a copolymer obtained by copolymerization at low pressure.
Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-nonene and 1-decene. , 1-dodecene and the like.

  Examples of the copolymerization method include ethylene and α-olefin polymerization methods such as a low pressure method, a slurry method, a solution method, and a gas phase method.

  The LLDPE used in the present invention has 3 to 25 short chain branches per 1000 carbon atoms as short chain branches, but is not distinguished from LDPE in that it does not have long chain branches exceeding about 20 carbon atoms. The Usually, in LLDPE, the structural unit derived from ethylene is about 99.9 to 90 mol%, and the structural unit derived from α-olefin is about 0.1 to 10 mol%. In the present invention, LLDPE prepared with a metallocene catalyst can be suitably used because of excellent structural uniformity.

Suitable LLDPE for use in the present invention includes “Sumikasen” manufactured by Sumitomo Chemical Co., Ltd.
In the present invention, as the EMAA constituting the EMAA layer in the sealant layer, one having a density of 0.93 to 0.94 g / cm ³ is preferably used from the viewpoint of adhesive strength with an adjacent layer. The MFR of EMAA is desirably 3 to 30 g / 10 minutes, more preferably 5 to 20 g / 10 minutes, from the viewpoint of processability in coextrusion. When MFR is smaller than 3 g / 10 min, co-extrusion with the cyclic polyolefin resin layer cannot be performed. In addition, said melt flow rate (MFR) is measured from the method based on JISK6922, and is a numerical value measured by 190 degreeC and 2.16kg load unless there is particular description.

The ratio of the structural unit derived from ethylene and the structural unit derived from methacrylic acid in EMAA can be arbitrarily determined by those skilled in the art depending on the type of the base material layer and the use of the lid. The more the proportion of structural units derived from ethylene, the lower the odor of the resin.
Examples of EMAA suitable for use in the present invention include “Nucrel N0908C” manufactured by Mitsui DuPont Polychemical Co., Ltd.
Furthermore, for the LLDPE layer and the EMAA layer, if necessary, one of additives such as an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, an antiblocking agent, a flame retardant, a crosslinking agent, and a colorant. You may add seed | species thru | or 2 or more types.

(3) Cyclic polyolefin resin layer In the present invention, the cyclic polyolefin resin constituting the cyclic polyolefin resin layer includes a ring-opening metathesis polymer (COP) obtained by polymerizing a cyclic olefin by a metathesis ring-opening polymerization reaction, and a cyclic olefin. And a copolymer of α-olefin (chain olefin), that is, cyclic olefin copolymer (COC).
As the cyclic olefin, any cyclic hydrocarbon having an ethylenically unsaturated bond and a bicyclo ring can be used, particularly those having a bicyclo [2.2.1] hept-2-ene (norbornene) skeleton. preferable.

Specifically, bicyclo [2.2.1] hept-2-ene and derivatives thereof, tricyclo [4.3.0.1 ^2.5 ] -3-decene and derivatives thereof, tricyclo [4.4.0.1 ^2.5] -3-undecene and derivatives thereof, tetracyclo [4.4.0.1 ^2.5 .1 ^7.10] -3-dodecene and derivatives thereof, pentacyclo ^{[6.5.1.1 3.6 .0 2.7 .0 9.13]} - 4 pentadecene and its derivatives, pentacyclo ^{[7.4.0.1 2.5 .1 9.12 .0 8.13]} -3- pentadecene and its derivatives, pentacyclo ^{[6.5.1.1 3.6 .0 2.7 .0 9.13]} - 4,10 penta decadiene and its derivatives, pentacyclo ^{[8.4.0.1 2.5 .1 9.12 .0 8.13]} -3- hexadecene and it derivatives, and the like, without limitation. The cyclic olefin may have a polar group such as an ester group, a carboxyl group, and a carboxylic anhydride group as a substituent.

  As the α-olefin copolymerized with the cyclic olefin, ethylene, an α-olefin having 3 to 20 carbon atoms can be used, and specifically, ethylene, propylene, 1-butene, 1-pentene, 3-methyl. Examples include -1-butene, 1-hexene, 4-methyl-1-pentene, and preferably ethylene.

  In the present invention, the production of the ring-opening metathesis polymer is not particularly limited as long as it is a known ring-opening metathesis polymerization reaction, and can be produced by ring-opening polymerization of the above cyclic olefin using a polymerization catalyst. .

In the production of the cyclic olefin copolymer, 25 to 45 mol% of α-olefin and 55 to 75 mol% of cyclic olefin are randomly polymerized using a single site catalyst such as a metallocene catalyst or a multisite catalyst. Is made by
Several ring-opening metathesis polymers and cyclic olefin copolymers preferably used in the present invention are commercially available. For example, “ZEONOR ^(R) ” manufactured by Nippon Zeon Co., Ltd. or manufactured by Polyplastics Co., Ltd. "TOPAS ^(R) " etc. are mentioned.

In addition, in order to obtain the more uniform film | membrane surface in the said cyclic polyolefin resin in order to suppress the generation | occurrence | production of the gel lump by aggregation of cyclic polyolefin resin at the time of film forming, It can be added arbitrarily within a range not impairing the non-adsorption property. The olefin-based resin may be any polyethylene or polypropylene having a melt flow rate (MFR) at 190 ° C. of 5 to 40 g / 10 minutes, preferably 15 to 30 g / 10 minutes. it can. Moreover, as an addition amount, it is good to mix | blend an olefin resin with the ratio of 3-50 mass% of the whole, Preferably 5-10 mass%.
If necessary, one or more additives such as an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, an antiblocking agent, a flame retardant, a crosslinking agent, and a colorant are added. May be.

(4) Anchor coat layer When LLDPE is used as a layer constituting the sealant layer, an anchor coat layer is provided on the synthetic resin layer in the first or second base material layer, and the sealant layer is laminated thereon. It is preferable to do. As such an anchor coat layer, any one can be used, for example, non-curing type such as polyolefin, organic titanate, polyethyleneimine, polybutadiene, isocyanate, polyester, acrylic, or the like, A curable anchor coating agent can be used. Moreover, as an anchor coat layer, it is preferable to use the anchor coat layer formed with the aqueous dispersion and epoxy resin composition which are explained in full detail below.

  The anchor coat layer formed by the aqueous dispersion contains an unsaturated carboxylic acid or an anhydride thereof in the range of 0.01 to 5% by mass, and the number average particle diameter is 1 μm or less, for example, 50 nm to An aqueous dispersion composed of polyolefin resin particles of 200 nm and substantially free of non-volatile aqueous additive such as emulsifier is applied and dried. This aqueous dispersion is described in JP-A-2004-9504, and is a polyolefin resin (A) composed of an unsaturated carboxylic acid or its anhydride, an olefin compound, and a (meth) acrylic ester. An aqueous dispersion and an aqueous dispersion of a polyester resin (B) having an anionic group of 20 to 700 (equivalent / 106 g) have a mass ratio of resin in each aqueous dispersion (A) / (B). = 90/10 to 20/80 and mixed and manufactured. In the above, examples of the unsaturated carboxylic acid or anhydride thereof include (meth) acrylic acid, maleic acid, itaconic acid, fumaric acid, crotonic acid and the like, and examples of the anionic group include a carboxyl group, A sulfonic acid group, a sulfuric acid group, a phosphoric acid group, etc. are mentioned. Specific examples of the aqueous dispersion include those commercially available from Unitika as Arrow Base SA-1200, SB-1200, SE-1200, TB-2010 and the like.

  Non-volatile aqueous additives such as emulsifiers remain in the coating film even after drying, and even if a small amount, it has a great effect on the adhesive interface, and decreases the adhesion and water resistance. In that case, a non-volatile aqueous additive such as an emulsifier is not added for the purpose of promoting aqueous formation or stabilizing the aqueous dispersion in the production process of the aqueous dispersion. For this reason, delamination does not occur, and it is excellent in adhesiveness with the 1st or 2nd base material layer, and also excellent in adhesiveness with a sealant layer.

The coating amount of the aqueous dispersion used to form the anchor coat layer, 0.1 g / m ² or less, more preferably 0.05 to 0.1 / m ^2. This is 1/10 or less compared to the amount of normal adhesive used, and the low molecular weight trace components contained in the aqueous dispersion hardly pass through the sealant layer, so that the aqueous dispersion The contained trace components do not leak into the contents, and the contents can be prevented from deteriorating.

  The anchor coat layer formed from the epoxy resin composition is a layer formed by curing a composition mainly composed of an epoxy resin composition composed of an epoxy resin and an epoxy resin curing agent. As said epoxy resin composition, what was described in Unexamined-Japanese-Patent No. 2003-155465 and Unexamined-Japanese-Patent No. 2007-126627 is mentioned, for example.

  Specifically, what consists of an epoxy resin and the epoxy resin hardening | curing agent which contains an aromatic site | part in a molecule | numerator can be used as said epoxy resin composition. Preferably, the epoxy resin composition used for the anchor coat layer is an epoxy resin composition containing an epoxy resin and an epoxy resin curing agent, and the formula ( An epoxy resin composition characterized by containing 40% by mass or more of the skeleton structure shown in 1) can be used.

  Furthermore, the epoxy resin composition is an epoxy resin composition containing an epoxy resin, an epoxy resin curing agent, and a curing accelerator, and is represented by the above formula (1) in the cured product formed from the resin composition. An epoxy resin composition characterized in that the content of the skeleton structure is 30% by mass or more can also be used.

  Examples of the epoxy resin include an epoxy resin having a glycidylamine moiety derived from metaxylylenediamine, an epoxy resin having a glycidylamine moiety derived from 1,3-bis (aminomethyl) cyclohexane, and a diaminodiphenylmethane derivative. Epoxy resin having glycidylamine moiety, epoxy resin having glycidylamine moiety and / or glycidyl ether moiety derived from paraaminophenol, epoxy resin having glycidyl ether moiety derived from bisphenol A, glycidyl derived from bisphenol F Epoxy resin having ether moiety, epoxy resin having glycidyl ether moiety derived from phenol novolac, glycidyl ether derived from resorcinol An epoxy resin having a site is exemplified. Among these resins, it is particularly preferable to use an epoxy resin having a glycidylamine moiety derived from metaxylenediamine. These resins can be used alone or in any combination of two or more.

  Moreover, as said epoxy resin hardening | curing agent, although the epoxy resin hardening | curing agent which can be used generally can be used, in order to further improve gas barrier property, the epoxy resin hardening | curing agent which contains an aromatic site | part in a molecule | numerator is used. It is preferable to use an epoxy resin curing agent containing the skeleton structure of the above formula (1) in the molecule. Specifically, metaxylylenediamine or paraxylylenediamine, and a modification reaction product with an epoxy resin or a monoglycidyl compound, a modification reaction product with an alkylene oxide having 2 to 4 carbon atoms, addition with epichlorohydrin A reaction product, a reaction product with a polyfunctional compound having at least one acyl group, which can form an amide group site by reaction with these polyamines to form an oligomer, by reaction with these polyamines It is more preferable to use a reaction product of a polyfunctional compound having at least one acyl group capable of forming an amide group site to form an oligomer and a monovalent carboxylic acid and / or a derivative thereof.

  Furthermore, when the adhesiveness between the first or second base material layer and the sealant layer is taken into account, as the epoxy resin curing agent, the following reaction products (A) and (B), or (A), It is particularly preferred to use the reaction products (B) and (C).

(A) Metaxylylenediamine or paraxylylenediamine
(B) A polyfunctional compound having at least one acyl group capable of forming an amide group site by reaction with a polyamine to form an oligomer
(C) C1-C8 monovalent carboxylic acid and / or derivative thereof

  Examples of the polyfunctional compound having at least one acyl group that can form an amide group site by reaction with the (B) polyamine to form an oligomer include acrylic acid, methacrylic acid, maleic acid, fumaric acid, succinic acid, Carboxylic acids such as malic acid, tartaric acid, adipic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid and their derivatives such as esters, amides, acid anhydrides, acid chlorides, etc., especially acrylic acid Methacrylic acid and derivatives thereof are preferred.

  In addition, monovalent carboxylic acids having 1 to 8 carbon atoms such as formic acid, acetic acid, propionic acid, butyric acid, lactic acid, glycolic acid, benzoic acid, and derivatives thereof such as esters, amides, acid anhydrides, acid chlorides, etc. The polyfunctional compound may be used in combination with the starting polyamine. The amide group site introduced by the reaction has a high cohesive force, and the presence of the amide group site in a high proportion in the epoxy resin curing agent results in higher oxygen barrier properties and good adhesion to various film materials. Strength is obtained.

  The curing accelerator is not particularly limited as long as it shortens the curing time or increases the low-temperature curability. For example, in addition to a boron trihalide complex or an organic acid, phenol, m-cresol, p -Chlorophenol, p-nitrophenol, 2,4-dinitrophenol, o-chlorophenol, 2,4-dichlorophenol, o-aminophenol, p-aminophenol, 2,4,5-trichlorophenol, resorcinol, hydroquinone Phenols such as catechol, phloroglicinol, bisphenol A, trisdimethylaminophenol; methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, ethylene glycol, 1,3-propane Alcohols such as all, glycerin, propylene glycol, thioglycenol, pentaerythritol, monoethanolamine, diethanolamine, triethanolamine and benzyl alcohol; imidazoles such as 2-ethyl-4-methylimidazole and 2-phenylimidazole; N- Ethylmorpholine, dibutyltin dilaurate, cobalt naphthenate, stannous chloride, triphenylphosphine, triphenyl phosphate, and the like can be used. Of these, boron trihalide complexes and organic acids are preferred. These curing accelerators can be used alone or in combination of two or more.

As the boron trihalide complex, a boron trifluoride complex is particularly preferable, and specifically, boron trifluoride amine complex such as boron trifluoride monoethylamine complex; boron trifluoride dimethyl ether complex, trifluoride Boron diethyl ether complex, boron trifluoride di-n-butyl ether complex and other boron trifluoride ether complexes; boron trifluoride phenol complex, boron trifluoride acetic acid complex, boron trifluoride methanol complex, trifluoride Boron piperidine complex, boron trifluoride tetrahydrofuran complex, boron trifluoride phosphate complex, boron trifluoride acetonitrile complex etc. are mentioned, especially boron trifluoride amine complex, especially boron trifluoride monoethylamine complex is suitable. Used. These boron trihalide complexes can be used alone or in combination of two or more.

  Organic acids include p-toluenesulfonic acid, m-xylenesulfonic acid, benzoic acid, p-toluic acid, p-aminobenzoic acid, p-chlorobenzoic acid, 2,4-dichlorobenzoic acid, salicylic acid, phthalic acid, isophthalic acid Acid, terephthalic acid, malic acid, oxalic acid, succinic acid, malonic acid, fumaric acid, maleic acid, tartaric acid, citric acid, formic acid, acetic acid, lactic acid, glycolic acid, n-butyric acid, iso-butyric acid, propionic acid, caproic acid , Octanoic acid, n-heptylic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid and the like, and p-toluenesulfonic acid is particularly preferably used. These organic acids can be used alone or in combination of two or more.

The anchor coat layer is a coating method such as gravure coating, roll coating, air knife coating, blade coating, short dwell, cast coating, etc. on the synthetic resin layer or sealant layer in the first or second base material layer. Can be formed by applying 0.01 to 0.1 g / m ^{2 of the} epoxy resin composition and drying.
As an epoxy resin composition suitable for use in the present invention, Epomin (anchor coat agent) manufactured by Nippon Shokubai Co., Ltd. may be mentioned.

(5) Method for Producing Sealant Layer The production of the sealant layer for a packaging material of the present invention is carried out by an arbitrary method. From the viewpoint of film formation stability, preferably, a cyclic polyolefin resin composition is produced by a coextrusion coating method. And LLDPE or EMAA by coextrusion coating on the synthetic resin layer in the first or second base material layer, or by melt coextrusion method (for example, T-die method, inflation method), etc. By a film forming method, a cyclic polyolefin resin composition and LLDPE or EMAA are coextruded to produce a multilayer sealant film, which is laminated with a laminate composed of first and second substrate layers.

  Further, as described above, when LLDPE is used as a layer constituting the sealant layer, an anchor coat layer is provided on the synthetic resin layer in the first or second base material layer, and the sealant layer is laminated thereon. It is preferable to do.

When the coextruded coating is performed on the synthetic resin layer in the first or second base material layer, or when the multilayer sealant film is laminated with the laminate comprising the first and second base material layers, the cyclic polyolefin resin The LLDPE layer or EMAA layer side surface and the synthetic resin layer are laminated so that the composition layer becomes the outermost layer in the laminate.
In particular, by coextrusion coating, the laminate composed of the first and second substrate layers, the LLDPE layer or the EMAA layer, and the adhesion between the LLDPE layer or the EMAA layer and the cyclic polyolefin resin composition layer Thus, it is possible to provide a sealant layer exhibiting higher sealing strength.

<6> Use The packaging material of the present invention can be made into a packaging bag by making a bag so that the sealant layer becomes the innermost layer. Moreover, a packaging container can be manufactured using the packaging material of the present invention as a cover material having a sealant layer as an innermost layer.
The packaging material of the present invention exhibits excellent non-adsorption properties, and exhibits good gas barrier properties and heat sealing properties. Therefore, laminates, packaging bags, and packaging containers having the same are particularly used for packaging pharmaceuticals, cosmetics, foods, and the like containing organic compounds as active ingredients, for example, coffee beans, rice, tea, beans, rice crackers, rice crackers. It can be suitably used as a packaging bag for dried foods such as foods or freeze-dried foods.
Next, the present invention will be specifically described with reference to examples.

[Example 1]
(1) Using a transparent vapor-deposited polyethylene terephthalate (PET) film (alumina vapor-deposited PET film) having a thickness of 12 μm, applying an adhesive for dry lamination on the vapor-deposited surface and using a diagonal plate with a plate depth of 90 μm, a coating amount of After coating at 0 g / m ² and bonding to the aluminum vapor-deposited surface of a 9 μm-thick aluminum vapor-deposited PET film, it was stored in a constant temperature bath at 40 ° C. for 48 hours to cure the adhesive.
(2) An anchor coating agent (Epomin manufactured by Nippon Shokubai Co., Ltd.) was applied to the PET surface of the aluminum vapor-deposited PET film at a coating amount of 0.4 g / m ² using a diagonal plate with a plate depth of 20 μm.
(3) Next, LLDPE (Sumikacene Hi-α CW8003 manufactured by Sumitomo Chemical Co., Ltd.) and cyclic olefin copolymer (TOPAS 8007F-500 manufactured by Polyplastics Co., Ltd.) The layers were laminated in this order by the extrusion coating method. Thereby, the laminated body which forms the packaging material of this invention was obtained. The layer structure of the resulting laminate was as follows:
Transparent vapor-deposited PET film (deposition surface) / adhesive / (deposition surface) Aluminum vapor-deposition PET film / anchor coating agent / LLDPE layer (20 μm) / cyclic polyolefin resin layer (5 μm)
In the description of the laminate in the present specification, “/” indicates that the left and right layers are laminated and integrated.

[Example 2]
In the formation of the sealant layer, an anchor coat agent was not used, and in addition to LLDPE, EMAA (Mitsui / DuPont Polychemical Co., Ltd. Nucrel N0908C) was used in the same manner as in Example 1, A laminate was produced.

[Comparative Example 1]
In the formation of the sealant layer, a laminate was produced in the same manner as in Example 1, except that LLDPE was used instead of the cyclic polyolefin resin.

[Comparative Example 2]
In the formation of the sealant layer, a laminate was produced in the same manner as in Example 1 except that LDPE was used instead of LLDPE.

[Comparative Example 3]
In the formation of the sealant layer, a laminate was produced in the same manner as in Example 1 except that a cyclic polyolefin resin was used instead of LLDPE.

[Evaluation methods and results]
(1) Adsorption test The laminates of Examples 1 and 2 and Comparative Examples 1 to 3 were cut into 10 cm × 10 cm squares, and their initial weights were measured.
A 10-liter stainless steel container was charged with 10 g of l-menthol solid, covered and filled with l-menthol vapor, and the cut laminate was suspended therein and stored at 40 ° C. for 7 days. .
After storage, the laminate was taken out, weighed, and the amount of l-menthol adsorbed was calculated from the difference from the initial weight.

(2) Seal strength test The laminates of Examples 1 and 2 and Comparative Examples 1 to 3 were overlapped with the base material layer facing outside, with a heat sealer (TP-701S HEAT SEAL TESTER manufactured by Tester Sangyo Co., Ltd.) Heat sealing was performed at 160 ° C. for 1 second at a pressure of 1 kgf / cm ² .
Subsequently, this was cut out into a strip shape having a width of 15 mm, and the sealed seal part was peeled off using a Tensilon tensile tester (RTC-1310A manufactured by Orientec Co., Ltd.), and the seal strength was measured. The tensile speed at this time was 300 mm / min.
The results are shown in the following table.

The laminates of Examples 1 and 2 and Comparative Examples 2 and 3 having a cyclic polyolefin resin composition layer tended to have a smaller amount of menthol adsorption than the laminate of Comparative Example 1.
Regarding the seal strength, the laminate of Comparative Example 3 having no LLDPE layer had a lower seal strength than the laminates of Examples 1 and 2.

1: First substrate layer 2: Second substrate layer 3: Sealant layer a: Synthetic resin layer b: Transparent barrier layer c: Metal barrier layer d: Synthetic resin layer e: LLDPE layer or EMAA layer f: cyclic Polyolefin resin layer

Claims (8)

A packaging material having at least a first base material layer having a transparent barrier layer and a synthetic resin layer, a second base material layer having a metal barrier layer and a synthetic resin layer, and a sealant layer,
The first base material layer and the second base material layer are laminated so that the transparent barrier layer and the metal barrier layer face each other.
The sealant layer has a linear low density polyethylene resin layer or an ethylene / methacrylic acid copolymer resin layer, and a cyclic polyolefin resin layer, and
The sealant layer and the first or second base material layer include a linear low density polyethylene resin layer or an ethylene / methacrylic acid copolymer resin layer in the sealant layer and the first or second base material layer. The packaging material, wherein the synthetic resin layers are laminated so as to face each other.   The sealant layer is composed of two layers of a linear low density polyethylene resin layer and a cyclic polyolefin resin layer, and the linear low density polyethylene resin layer is a first or second group via an anchor coat layer. It is laminated | stacked on the synthetic resin layer in a material layer, The packaging material of Claim 1 characterized by the above-mentioned.   The anchor coat layer is an aqueous dispersion in which a polyolefin copolymer resin containing 0.01 to 5% by mass of an unsaturated carboxylic acid or an anhydride thereof is dispersed so that the number average particle diameter thereof is 1 μm or less, and An aqueous dispersion formed so as not to substantially contain a nonvolatile aqueous solubilizing aid in the aqueous dispersion is applied to the surface of the synthetic resin layer of the first base material layer or the second base material layer at the time of drying. The packaging material according to claim 2, wherein the packaging material is formed by coating, heating and drying so as to have a thickness of 0.1 to 2 µm.   The packaging material according to claim 2, wherein the anchor coat layer is a layer formed by curing a composition mainly composed of an epoxy resin composition comprising an epoxy resin and an epoxy resin curing agent.   The packaging material according to claim 1, wherein the sealant layer is a layer composed of two layers of an ethylene / methacrylic acid copolymer resin layer and a cyclic polyolefin resin layer.   The packaging material according to any one of claims 1 to 5, wherein the transparent barrier layer is formed of an inorganic oxide selected from the group consisting of silicon oxide, magnesium oxide, and aluminum oxide.   The metal barrier layer is formed of a metal or an alloy selected from the group consisting of aluminum, copper, zinc, gold and silver and alloys thereof. Packaging material.   The packaging material according to any one of claims 1 to 7, wherein the linear low-density polyethylene resin layer and the cyclic polyolefin-based resin composition layer are laminated by coextrusion coating.

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