JP4534658B2 - Gas barrier film laminate - Google Patents

Description

  The present invention relates to a laminate used in the field of packaging foods, beverages, non-food products such as pharmaceuticals and electronic parts, medical instruments and members, electronic members themselves, etc. The present invention relates to a gas barrier film laminate that blocks contents from oxygen and water vapor and suppresses deterioration and alteration.

  In recent years, packaging materials used in the field of non-food products such as food and beverages, pharmaceuticals, and electronic parts suppress the deterioration of contents, and retain the functions and properties of medical instruments, members, and electronic members themselves. Therefore, it is necessary to prevent the influence of oxygen or water vapor that permeates the material or other gas that alters the contents, and it is required to have gas barrier properties that block these gases.

  Therefore, as a conventional gas barrier layer, a metal foil typified by aluminum or the like, a vapor deposition film of aluminum or an inorganic oxide, a resin film such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinylidene chloride, polyacrylonitrile, or the like. A plastic film coated with a resin has been mainly used.

  Among them, some contents require a super gas barrier function, and the gas barrier materials are often combined and used together.

  However, when the base material having excellent gas barrier properties, or the base material having gas barrier properties at two or more locations in the same laminate using an adhesive, dry or non-solvent laminating, heating the adhesive, etc., and curing the reaction, Carbon dioxide gas is generated during or after processing due to the influence of moisture in the base material or the atmosphere, and it does not escape within the gas barrier base material, resulting in a foam whitening state. This is a serious problem in appearance and also causes a problem in the laminate strength between the gas barrier substrates.

  As a technique for solving such a problem, when performing dry or non-solvent lamination, a method of reacting and curing at room temperature is employed instead of heat curing the adhesive. However, not in the case of light packaging materials, but in the case of packaging materials that are heated or heat and pressure sterilized or filled with heavy objects, there is also a need to strengthen the adhesive strength in medical instruments, members, electronic members, etc. It is essential to cure for at least 2 days in a heating environment of about 40 ° C. or higher.

  Also, if the substrates can be bonded to each other by a method other than dry or non-solvent lamination, for example, an adhesive is applied on the substrate side at a low coating amount, and the resin is then extruded in a molten state and bonded. The above problem does not occur if an extrusion method or a thermal laminating method in which an adhesive resin having a polar functional group is applied between base materials and pressure-bonded with a roll heated at a high temperature is used. However, in the former extrusion method, the required quality is often not satisfied in the case of heating, heat and pressure sterilization treatment, or in the case of packaging materials that are filled with heavy objects. There are problems that the base material that can withstand the roll temperature is limited, the laminating speed is low, and the manufacturing machine is expensive.

The present invention is intended to solve the problems of the prior art. By considering the adhesive composition, the conventional dry or non-solvent laminating method can be used as it is, and substrates having gas barrier properties can be used. It aims at providing the gas barrier film laminated body characterized by not foaming whitening by the influence of a water | moisture content even when it bonds together.

Invention of Claim 1 is metal foil, a metal vapor deposition film, an inorganic oxide vapor deposition film, a polyvinyl alcohol film, an ethylene-vinyl alcohol copolymer film, a polyvinylidene chloride film, a polyacrylonitrile film, or polyvinyl alcohol or ethylene-vinyl. A compound in which a plurality of base materials having gas barrier properties are formed of any base material selected from an alcohol copolymer or a plastic film coated with polyvinylidene chloride or polyacrylonitrile, and wherein the amino group is protected with a ketone group; and It is a gas barrier film laminate that is bonded by a dry lamination method or a non-solvent lamination method using an adhesive that is cured by a reaction with a compound having an epoxy group.

Invention of Claim 2 is metal foil, metal vapor deposition film, inorganic oxide vapor deposition film, polyvinyl alcohol film, ethylene-vinyl alcohol copolymer film, polyvinylidene chloride film, polyacrylonitrile film, or polyvinyl alcohol or ethylene-vinyl. A compound in which a plurality of base materials having gas barrier properties are formed of any base material selected from an alcohol copolymer or a plastic film coated with polyvinylidene chloride or polyacrylonitrile, and wherein the amino group is protected with a ketone group; and gas barrier film laminate der, characterized by being bonded by dry lamination or non-solvent lamination method using an adhesive which is cured by reaction with a carboxylic acid or carboxylic acid chloride or carboxylic acid anhydride .

Invention of Claim 3 is said gas barrier film laminated body, Comprising: At least 1 of said several base materials has formed the vapor deposition layer which consists of a metal or an inorganic oxide on a film, On said vapor deposition layer, A base material provided with a gas barrier deterioration preventing layer containing a water-soluble polymer and at least one of a metal alkoxide, a silane coupling agent, a silane monomer, a hydrolyzate of a silane monomer, and tin chloride. This is a gas barrier film laminate.

Invention of Claim 4 is said gas barrier film laminated body, Comprising: At least 1 is provided with the primer layer which consists of a combination of an acrylic polyol, an isocyanate compound, and a silane coupling agent on a film among several said base materials. a gas barrier film laminate, wherein the a plug i Mar layer substrate deposited layer made of metal or inorganic oxide is formed on.

Invention of Claim 5 is said gas barrier film laminated body, Comprising: The heat seal layer which consists of a polyolefin base material which can be heat-sealed on the outer surface of said several base material adhere | attached using the said adhesive agent is laminated | stacked. a gas barrier film laminate, characterized in that there.

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According to the present invention, when there are two or more base materials having gas barrier properties against oxygen, water vapor, or the like, or when two or more base materials having gas barrier properties exist in the same laminate, they are subjected to a dry or non-solvent lamination method. Thus, it is possible to provide a packaging material that does not foam white due to the influence of moisture generated in the laminated body even when heat-cured for reaction curing when bonded using an adhesive. In particular, when a transparent film imparted with a gas barrier property is used, the problem of poor appearance cannot be avoided, so the effect of the present invention can be said to be great.

  As described above, according to the present invention, substrates having gas barrier properties against oxygen, water vapor, or the like, or two or more substrates having gas barrier properties in the same laminate are dried. Or, when bonding by non-solvent laminating method, it is not a mechanism that cures by reaction of isocyanate groups and hydroxyl groups, or moisture in the environment, but protects them with amino groups or imino groups or aldehyde groups or ketone groups, for example. If it is cured by the reaction of the compound with an epoxy group-containing compound, carboxylic acid, carboxylic acid chloride or carboxylic acid anhydride, it will be generated in the laminate even if it is heat-cured for reaction curing. It is possible to provide a packaging material that does not foam white due to the influence of moisture. Also, it withstood retort sterilization under high temperature and high pressure, and no influence on the gas barrier properties thereafter. In particular, when a transparent film imparted with a gas barrier property is used, the phenomenon of foaming whitening is a big problem as a poor appearance, and thus the effect of the present invention can be said to be great.

  The present invention will be described in detail with reference to the drawings. FIG. 1 is a cross-sectional view showing an example of the gas barrier film laminate of the present invention. Of course, the present invention is not limited to this, and various material configurations can be considered.

First, in FIG. 1, 1 is a base material 1, 2 is a primer layer A, 3 is a vapor deposition layer B, 4 is a gas barrier property deterioration preventing layer C, and base materials 1 and 2 are base materials made of a plastic material. The material 1 is a primer layer A, 5 is a base material 2, 6 is a vapor deposition layer D, 7 is a base material 3, 8 and 9 are adhesive layers. The base materials 1 and 2 are base materials made of a plastic material. The base material 1 is sequentially laminated with a primer layer A, a vapor deposition layer B made of a metal or an inorganic oxide, and a gas barrier property deterioration preventing layer C. Similarly, a layer made of a metal or an inorganic oxide is deposited on the substrate 2, and a heat-sealable polyolefin substrate 3 is laminated on the opposite side of the deposited layer D. To the substrate 2, it may be provided as necessary gas barrier property deterioration preventing layer on the primer layer and deposition layer D in addition to the vapor deposition layer D. The adhesive of the present invention is applied between the layers of the substrates 1 and 2, but the adhesive used between the layers of the substrates 2 and 3 is not limited thereto.

  The base materials 1 and 2 described above are preferably made of a plastic material and transparent. For example, polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyamide films such as 6, 6-nylon, polyolefin films such as polyethylene and polypropylene, polystyrene films, polycarbonate films, polyacrylonitrile films, polyimide films, etc. An engineering plastic film or the like is used, which may be stretched or unstretched, and preferably has mechanical strength and dimensional stability. In particular, a film arbitrarily stretched in the biaxial direction among these is preferably used, and when it is used for a packaging material, it is biaxially stretched in consideration of gas barrier properties, filling suitability, texture, easy disposal, and price. A polyester film (PET) or a polyamide film is preferable.

  The thicknesses of the base materials 1 and 2 are not particularly limited, but in consideration of suitability as a packaging material and processability, the thickness is practically in the range of 3 to 200 μm, and generally 6 to 30 μm. It can be said that it is more preferable.

Further, various well-known additives and stabilizers such as antistatic agents, plasticizers, lubricants, antioxidants and the like may be used on the surfaces of the substrates 1 and 2 to improve adhesion. Therefore, corona treatment, plasma treatment, ozone treatment or the like may be performed as pretreatment, and further chemical treatment or solvent treatment may be performed. In particular, the plasma treatment is preferable because the adhesion between the substrate surface and the vapor deposition layer B made of a metal or an inorganic oxide to be laminated next is strengthened.

  In addition, when the primer layer A is provided between the base material 1 and the vapor deposition layer B, a vapor deposition layer made of a metal or an inorganic oxide is uniformly formed to improve the gas barrier property, and the adhesiveness is greatly improved. When performing a retort sterilization process etc., it is preferable to provide a primer layer. The primer layer is an organic polymer obtained by a two-component reaction of an isocyanate compound with a polyol such as acrylic polyol, polyvinyl acetal, polyester polyol or polyurethane polyol, or an organic compound having a urea bond by reaction with a polyisocyanate compound and water. , Polyethyleneimine or derivatives thereof, polyolefin emulsions, polyimides, melamines, phenols, or inorganic silicas such as organically modified colloidal silica, organic silane compounds such as silane coupling agents and hydrolysates thereof, etc. Any of them can be used as a primer agent, but a combination of an acrylic polyol, an isocyanate compound, and a silane coupling agent is particularly preferable. In general, it is desirable to coat so that the thickness after drying is in the range of 0.005 to 5 μm, and more preferably in the range of 0.01 to 1.0 μm. When the thickness is 0.01 μm or less, it is difficult to obtain a uniform coating film from the viewpoint of coating technique, and conversely, when it exceeds 1 μm, it is uneconomical.

  The former of the vapor deposition layer B made of a metal or an inorganic oxide includes aluminum, tin, nickel, cobalt, chromium, etc., and the latter is an oxide of silicon, aluminum, titanium, zirconium, tin, magnesium, or a mixture thereof, nitrogen. And a unit of fluoride or a composite thereof, and is formed by a vacuum process such as a vacuum deposition method, a sputtering method, or a plasma vapor deposition method. In particular, aluminum oxide is colorless and transparent, excellent in water resistance by boil / retort sterilization treatment, and can be used for a wide range of applications.

  The film thickness of the vapor deposition layer B varies depending on the material type and application used, and the film thickness of the primer layer A, but generally it is preferably in the range of 5 to 300 nm, preferably 10 to 150 nm.

Further, it is a gas barrier property deterioration preventing layer (overcoat layer) C provided on the vapor-deposited thin film layer. This is a water-soluble polymer and one or more kinds of metal alkoxides, silane coupling agents, silane monomers, and hydrolysates thereof. Alternatively, an aqueous solution containing at least one of tin chloride or a water / alcohol mixed solution is used as a main component, and this solution is applied onto a vapor-deposited thin film layer made of a metal or an inorganic oxide and then dried by heating.
The water-soluble polymer in the gas barrier property deterioration-preventing coating layer is preferably polyvinyl alcohol, starch, or cellulose. In particular, when polyvinyl alcohol (hereinafter referred to as PVA) is used for the coating agent of the present invention, the gas barrier property is most excellent. Because PVA is a polymer containing the most hydroxyl groups in the monomer unit, it has a very strong hydrogen bond with the remaining silanol groups. PVA as used herein is generally obtained by saponifying polyvinyl acetate, and saponification of saponification in which only several percent of acetyl groups remain from so-called partially saponified PVA, in which several acetyl groups remain. Includes up to PVA. The molecular weight of PVA has various degrees of polymerization ranging from 300 to several thousand, but there is no problem in the effect even if any molecular weight is used. However, it can be said that PVA having a high molecular weight and a high polymerization degree is generally preferable because of high water resistance.

  The thickness of the mixed coating solution after drying is not particularly limited. However, if the thickness exceeds 50 μm or more, cracks are likely to occur. Therefore, the thickness is preferably 0.01 to 50 μm.

As a gas barrier film layer forming method, a normal coating method can be used. For example, dipping method, roll coating, gravure coating, reverse coating, air knife coating, comma coating, die coating, silk screen, spray coating, gravure offset method and the like can be used. Using these coating methods, coating is performed on the deposited layer or directly on the substrate.

  Any method can be used for drying the gas barrier deterioration preventing coating layer by heating the gas barrier coating layer such as hot air drying, hot roll drying, high frequency induction heating, infrared irradiation, UV irradiation, etc. Two or more of these may be combined.

  By providing a heat seal layer as the base material 3, a more practical packaging material can be provided. The heat seal layer is used for an adhesive part when forming a bag-like package or the like. For example, polyethylene, linear polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer Resins such as ethylene-methacrylic acid ester copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, and metal cross-linked products thereof are used. The thickness is determined according to the purpose, but is generally in the range of 15 to 200 μm. Moreover, you may provide a heat seal layer on the opposite side to the vapor deposition layer of the base material 1 with the shape of a package.

  As a method for forming the heat seal layer, a dry or non-solvent laminating method in which a film made of the above-mentioned resin is bonded with the present invention or a general adhesive, the above-mentioned resin is heated and melted and extruded into a curtain shape and bonded. Both the extrusion laminating method and the knee laminating method can be formed by a known laminating method.

  It is possible to decorate the print layer on the gas barrier deterioration-preventing coating layer or vapor-deposited layer as necessary, and the print layer or adhesive is also provided on the surface opposite to the vapor-deposited surface of the substrate 1. A plurality of resins can be laminated. In addition, the same process can be applied to the lamination of other base materials having a gas barrier property.

  Hereinafter, the gas barrier laminate of the present invention will be described with reference to specific examples.

(1) Thickness; 12 [mu] m PET / primer layer / aluminum oxide layer / gas barrier property deterioration preventing layer (2) thickness; 15 [mu] m ONy / primer layer / silicon oxide layer (3) thickness; 70 [mu] m CPP
(1) to (2) Interlayer adhesive Main agent; Polyether-isophoronediamine MEK protector / curing agent; Epichlorohydrin trimethylolpropane (TMP) adduct (2) to (3) Interlayer adhesive; Main agent Polyester polyester / curing agent; trimethylolpropane adduct of xylylene diisocyanate (XDI) and IPDI mixture

(4) Thickness; 12 [mu] m PET / primer layer / silicon oxide layer / gas barrier property deterioration preventing layer (5) thickness; 15 [mu] m EVOH (Kuraray Co., Ltd.; EF-CR)
(6) Thickness: 60 μm LLDPE
(4) to (5) Interlayer adhesive Main agent: Acetone protector / curing agent of polyether-xylylenediamine; Trimethylolpropane (TMP) adduct of epichlorohydrin (5) to (6) Interlayer adhesive Main agent Polyester-polyurethane system / curing agent; trimethylolpropane adduct of IPDI and XDI mixture

As a comparative example for comparing with the performance of the gas barrier laminate of the present invention obtained in Example 1, in Example 1, (1) to (2) the interlayer adhesive was changed to (2) to (3) the interlayer adhesive. The same except for the replacement.

  As a comparative example for comparison with the performance of the gas barrier laminate of the present invention obtained in Example 2, in Example 2, (4) to (5) the interlayer adhesive was changed to (5) to (6) interlayer adhesive. The same except for the replacement.

  Dry lamination was performed using the above adhesive, curing was performed at 50 ° C. for 4 days, the appearance of the obtained gas barrier film laminate was confirmed, and evaluation as various packaging materials was performed. In addition, each was subjected to a retort sterilization treatment at 121 ° C. for 30 minutes, and the oxygen permeability before and after the treatment was measured using an oxygen permeability measuring device (OXTRAN-2 / 20 manufactured by Modern Control) in 30 ° C. × 70% RH. Measured under atmosphere. The results are shown in Table 1.

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  From Table 1, the gas barrier film laminates of Examples 3 and 4 as comparative examples for comparison with the performance of the gas barrier laminate of the present invention were confirmed to be foamed and whitened between the gas barrier substrates. In the gas barrier laminate of the present invention obtained in 2, no problem was observed in appearance. In addition, no significant difference was observed in oxygen barrier properties, and a high barrier was maintained without barrier deterioration even after retort sterilization.

It is sectional drawing which shows an example of the gas barrier film laminated body of this invention.

Explanation of symbols

1 ... Base material 1
2 ... Primer layer A
3 ... deposition layer B
4 ... Gas barrier property deterioration prevention layer C
5 ... Base material 2
6 ... deposition layer D
7 ... Base material 3
8, 9 ... Adhesive layer

Claims (5)

Metal foil, metal vapor deposition film, inorganic oxide vapor deposition film, polyvinyl alcohol film, ethylene-vinyl alcohol copolymer film, polyvinylidene chloride film, polyacrylonitrile film, or polyvinyl alcohol or ethylene-vinyl alcohol copolymer or polychlorination A plurality of base materials having a gas barrier property comprising a base material selected from plastic films coated with vinylidene or polyacrylonitrile, wherein a compound having an amino group protected with a ketone group and a compound having an epoxy group A gas barrier film laminate that is bonded by a dry lamination method or a non-solvent lamination method using an adhesive that cures by reaction. Metal foil, metal vapor deposition film, inorganic oxide vapor deposition film, polyvinyl alcohol film, ethylene-vinyl alcohol copolymer film, polyvinylidene chloride film, polyacrylonitrile film, or polyvinyl alcohol or ethylene-vinyl alcohol copolymer or polychlorination A compound in which a plurality of base materials having gas barrier properties are made of any one of base materials selected from plastic films coated with vinylidene or polyacrylonitrile, and in which an amino group is protected with a ketone group, and a carboxylic acid or a carboxylic acid chloride Alternatively, a gas barrier film laminate that is bonded by a dry lamination method or a non-solvent lamination method using an adhesive that cures by reaction with a carboxylic acid anhydride. At least one of the plurality of base materials has a vapor deposition layer made of a metal or an inorganic oxide formed on the film, and the water-soluble polymer, one or more types of metal alkoxide, silane coupling are formed on the vapor deposition layer. 3. The gas barrier film laminate according to claim 1, wherein the gas barrier film laminate is provided with a gas barrier deterioration preventing layer containing at least one of an agent, a silane monomer, a hydrolyzate of silane monomer, and tin chloride. . Wherein at least one of the plurality of substrates, on the film, an acrylic polyol with an isocyanate compound, a primer layer comprising a combination of a silane coupling agent provided a vapor deposition layer made of a metal or an inorganic oxide on the plug i Mar layer The gas barrier film laminate according to any one of claims 1 to 3, wherein the gas barrier film laminate is a substrate on which is formed.   The heat sealing layer which consists of a polyolefin base material which can be heat-sealed on the outer surface of the said several base material adhere | attached using the said adhesive agent is laminated | stacked, The any one of Claim 1 thru | or 4 characterized by the above-mentioned. The gas barrier film laminate according to the description.

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