JP2001171034A - Laminated material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inexpensive laminated material excellent in gas barrier properties against oxygen gas and steam, especially, oxygen gas barrier properties and also excellent in transparency, flexibility or the like. SOLUTION: A laminated material is constituted by providing a first gas barrier membrane based on inorganic oxide on one surface of a stretched base material film by a plasma chemical vapor deposition method while providing a second barrier film based on inorganic oxide on one surface of a heat-sealable base material film by a plasma chemical vapor deposition method and laminating both base material films through a laminating adhesive layer due to a dry lamination method or a melt extrusion resin layer due to an extrusion lamination method so that the first and second films are opposed to each other.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated material, and more particularly, to a gas barrier property against oxygen gas, water vapor gas and the like, particularly excellent in gas barrier property against oxygen gas, and further excellent in transparency and flexibility. It relates to an inexpensive laminated material.

[0002]

2. Description of the Related Art Conventionally, various packing materials have been developed and proposed for filling and packaging various articles such as food and drink, pharmaceuticals, chemicals, daily necessities, miscellaneous goods, and the like.
In order to prevent the contents from deteriorating or the like, the above-mentioned packaging material is strongly required to have mainly a barrier property against oxygen gas or water vapor gas, that is, a so-called gas barrier property. By the way, as a barrier material against oxygen gas or water vapor gas, for example, aluminum foil, or a polypropylene resin film, a polyester resin film, or a polyamide resin film, etc. Aluminum vapor-deposited resin film formed by vapor-deposition, furthermore, polyvinylidene chloride-based resin or vinylidene chloride and other monomers
And a resin film in which the above-mentioned polyvinylidene chloride-based resin is coated on the surface of a resin film or a polypropylene-based resin film, a polyester-based resin film, or a polyamide-based resin film, or a polyvinyl alcohol-based resin. For example, using a physical vapor deposition (PVD) method such as a vacuum evaporation method on one surface of a base film such as a plastic film or a film made of ethylene-vinyl alcohol copolymer, For example, a silicon oxide, an aluminum oxide, or the like is formed by using a vapor deposition film provided with a vapor deposition film of an inorganic oxide such as silicon oxide or aluminum oxide, or a chemical vapor deposition method (CVD method) such as a low-temperature plasma chemical vapor deposition method. A vapor deposition film provided with a vapor deposition film of an inorganic oxide is known. These barrier materials are made of other plastic films or
It provides a packaging material that is laminated with a paper base material and other materials to be useful for filling and packaging various articles such as foods and drinks, pharmaceuticals, chemicals, daily necessities, miscellaneous goods, and the like.

[0003]

However, the above-mentioned barrier materials have oxygen gas barrier properties, water vapor gas barrier properties, etc., and can be expected to have a certain effect. The fact is that it is not satisfactory enough. For example, the above-mentioned aluminum foil is a gas barrier material having an excellent gas barrier property against oxygen gas, water vapor gas, and the like.
In addition to the problem of disposal after use, there is also the problem that the contents cannot be visually recognized from the outside in the packaged product filled with the contents because it is basically an opaque material. There is. Next, the above-mentioned polypropylene-based resin film, polyester-based resin film, or aluminum-deposited resin film obtained by vacuum-depositing aluminum on a polyamide-based resin film or the like by a vacuum deposition method or the like is similar to the above-described aluminum foil. In addition, not only is there a problem that the contents cannot be visually recognized from outside after disposal treatment after use, but also the gas barrier property is inferior to aluminum foil, so that it is not necessarily a satisfactory barrier material.

Further, a film made of the above-mentioned polyvinylidene chloride resin or a copolymer resin of vinylidene chloride and another monomer, a polypropylene resin film, a polyester resin film, a polyamide resin film or the like is used. Resin films coated with polyvinylidene chloride-based resin are widely used as resin-based barrier materials, but are preferred in terms of environmental protection because they generate chlorine-based gas in incineration treatment after use. In addition, since it is a resin-based material, gas barrier properties are not always sufficient, and it cannot be used for filling and packaging contents that require a high level of barrier properties. Next, a film made of the above polyvinyl alcohol or ethylene-vinyl alcohol copolymer shows relatively excellent oxygen gas barrier properties under absolutely dry conditions, but has insufficient steam gas barrier properties, and Under a humidity condition, the oxygen gas barrier property is remarkably deteriorated, and it cannot be said that the barrier material is sufficiently satisfactory under a practical condition. In order to improve the above-described humidity dependency, various methods and the like have been developed and proposed. For example, a method of depositing a deposited film of an inorganic oxide such as silicon oxide using a vacuum deposition method or the like. However, under high humidity conditions of 70% or more, deterioration of the oxygen gas barrier property cannot be improved (see JP-A-4-7139).

Next, on one surface of the above-mentioned base film such as a plastic film, an inorganic material such as silicon oxide, aluminum oxide or the like is formed by a physical vapor deposition method (PVD method) such as a vacuum evaporation method. Basically, with respect to a vapor-deposited film provided with a vapor-deposited oxide film, it is basically possible to form a vapor-deposited film on any of the base films by a vacuum vapor deposition method or the like. The remarkable effect is related to the heat resistance of the base film.
For example, when a heat-resistant base film such as a polyethylene terephthalate film is used as the base film, a vapor-deposited film is formed by a vacuum vapor-deposition method or the like, and the gas barrier property against oxygen gas is greatly improved. It can be expected. However, as the base film, for example, a biaxially stretched polypropylene film, a non-stretched polypropylene film, or when using a base film having poor heat resistance such as a low-density polyethylene film, a vapor-deposited film is formed by a vacuum vapor deposition method or the like. Although formation is technically possible, it is difficult to achieve a significant improvement effect such as gas barrier property against oxygen gas, and it can be said that it is not always satisfactory. Not something. Further, as the above base film,
For example, when using a polyethylene terephthalate film, the polyethylene terephthalate film is
There is a problem that it has rigidity, is hard, and easily generates film wrinkles and the like, and thus is not suitable for packaging materials requiring flexibility and the like.

Further, a chemical vapor deposition (CVD) method such as a low-temperature plasma-enhanced chemical vapor deposition (CVD) method is applied to one surface of the base film such as the plastic film to form, for example, silicon oxide or aluminum oxide. With respect to a vapor-deposited film provided with an inorganic oxide vapor-deposited film, when forming the vapor-deposited film, the thermal damage to the base film is small, and the inorganic oxide vapor-deposited film can be formed on various plastic films. In addition, the deposited film has various advantages such as good bending resistance and little reduction in barrier property even when subjected to mechanical stress, and has attracted much attention in recent years. For example, there has been proposed a method of forming a deposited film of silicon oxide on a polyolefin resin molded product having poor heat resistance by using a plasma enhanced chemical vapor deposition method (Japanese Patent Laid-Open No. 5-2).
87103). However, in the above method, after laminating the sealant film,
The oxygen gas barrier property is 5 cc / m ² · day · atm or more, and in fact, it is not always possible to achieve a sufficiently satisfactory oxygen gas barrier property. In the above, in order to improve the oxygen gas barrier properties, for example, it has been attempted to form a deposited film of an inorganic oxide to a thickness of 1000 ° or more. It is necessary to solve the problem of the strength deterioration of the inferior polyolefin resin film due to the plasma reaction. Further, when the thickness of the deposited film of the inorganic oxide is increased, the deposited film itself exhibits a yellow tint, and when used as a packaging material for filling and packaging foods and drinks, there is a problem that the commercial product is affected. There are points. In general, polyolefin-based resin films are inexpensive, and even after use, there is no problem in disposal treatment. For this reason, a polyolefin-based resin film is currently used as a base film, For example, the development of a barrier material formed with a gas barrier film or the like such as a vapor-deposited film of an inorganic oxide has been studied in various ways, but a practical method has not yet been developed. is there. Accordingly, an object of the present invention is to provide an inexpensive laminated material that is excellent in gas barrier properties against oxygen gas, water vapor, and the like, particularly excellent in oxygen gas barrier properties, and further excellent in transparency, flexibility, and the like.

[0007]

As a result of various studies to solve the above-mentioned problems, the present inventor focused on a vapor-deposited thin film having excellent bending resistance by a plasma enhanced chemical vapor deposition method.
On one surface of the stretched base film, a first barrier thin film mainly composed of an inorganic oxide formed by a plasma-enhanced chemical vapor deposition method is provided. On the other hand, on one surface of a heat-sealing base film,
The second mainly composed of inorganic oxide by plasma-enhanced chemical vapor deposition
Is provided, and the above-mentioned stretched base film and heat-sealing base film are arranged such that the first barrier thin film surface and the second barrier film surface face each other, A laminated material is manufactured by laminating through an adhesive layer for laminating by a dry laminating method or a resin layer extruded by a laminating method by an extruding laminating method, and the laminated material is used. To produce a packaging container by bag making or box making, in the packaging container, for example, food and drink, pharmaceuticals, chemicals,
Various products such as daily necessities, miscellaneous goods, etc. are filled and packaged to produce a packaged product. The first and second barrier thin films have bending resistance, excellent flexibility, etc. ,
Further, in the case of bag making or box making, etc., the first and second
No occurrence of cracks or the like is observed in the barrier thin film, and has extremely excellent laminating suitability, suitability for bag making, etc., and as a result, gas barrier properties against oxygen gas, water vapor, etc.,
Excellent gas barrier properties against oxygen gas, alteration of contents,
Prevents modification, etc. and has stable long-term distribution and storage suitability, and is excellent in transparency, so that the contents can be visually recognized from the outside and extremely excellent and good packaging The present invention has been accomplished by finding a useful laminated material that can be manufactured at low cost.

That is, according to the present invention, a first barrier thin film mainly composed of an inorganic oxide is provided on one surface of a stretched base film by a plasma enhanced chemical vapor deposition method.
A second barrier thin film mainly composed of an inorganic oxide formed by a plasma-enhanced chemical vapor deposition method on one surface of the stretchable base film, and further comprising the stretched base film and the heat-sealing base film With the first barrier thin film surface and the second barrier film surface facing each other, and a laminating adhesive layer formed by a dry laminating method or a melt extruded resin layer formed by an extruding laminating method. And to a laminated material characterized by being laminated through the above.

The present invention will be described in more detail below. The layer structure of the laminated material according to the present invention will be described more specifically with reference to the drawings.
FIG. 2 is a schematic cross-sectional view illustrating one example of a layer configuration of a laminated material according to the present invention. First, as shown in FIG. 1, a laminated material 1 according to the present invention is provided with a first barrier thin film 3 mainly composed of an inorganic oxide formed on one surface of a stretched base film 2 by a plasma chemical vapor deposition method. On the other hand, on one surface of the heat-sealing base material film 4, a second barrier thin film 3 mainly composed of an inorganic oxide formed by a plasma-enhanced chemical vapor deposition method is provided.
a. Further, the above-mentioned stretched base film 2 and heat-sealing base film 4 are combined with the first barrier thin film 3.
A configuration in which the surface and the second barrier film 3a face each other and are laminated via a lamination adhesive layer 5 by a dry lamination method or a melt-extruded resin layer 5a by an extrusion lamination method. Is a basic structure. Next, when the laminated material according to the present invention is exemplified by a laminated material having another form, as the laminated material 1a, as shown in FIG. 2, in the laminated material 1 shown in FIG. Directly on the barrier thin film 3 or
One having a configuration in which a print pattern layer 6 is provided via a primer agent layer (not shown) using a print primer agent can be given. In the figures, 1, 2, 3, 3a, 4,
5, 5a have the same meaning as described above. The above-mentioned illustrations illustrate one or two examples of the laminated material according to the present invention, and the present invention is not limited thereto.

Next, in the present invention, the material, material, manufacturing method and the like constituting the laminated material according to the present invention will be described. First, as a stretched base film constituting the laminated material according to the present invention, for example, Polypropylene homopolymer by propylene homopolymer, polypropylene resin such as propylene-α-olefin copolymer obtained by random or block copolymerization of α-olefin containing propylene as main component, polyethylene terephthalate, polyethylene It is made of a polyester resin such as naphthalate or a polyamide resin such as nylon 6, nylon 66, nylon 610, nylon 12, or MXD nylon (trade name, manufactured by Mitsubishi Gas Chemical Industry Co., Ltd.).
In the present invention, a method of forming a film of these resins alone, or a method of forming a multilayer co-extrusion film using two or more of the same resin, and further, using two or more of the same resin, Polypropylene-based resin, polyester-based resin, or a polyamide-based resin film or sheet is manufactured by a method of mixing and forming a film before forming a film, and further, for example, a tenter method, or , A polypropylene-based resin, a polyester-based resin, which is stretched in a uniaxial or biaxial direction by using a tuber method or the like.
Alternatively, a polyamide resin film or sheet can be used. The thickness of the stretched base film is about 5 to 100 μm, more preferably 10 to 5 μm.
About 0 μm is desirable.

[0011] Next, in the present invention, the heat-sealing base material filler constituting the laminated material of the present invention may be any material that can be melted by heat and can be fused to each other. High density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene,
Single-site catalyst, for example, polyethylene or polypropylene polymerized using a metallocene catalyst, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene -Polyolefin resins such as methacrylic acid copolymer, ethylene-propylene copolymer, methylpentene polymer, polyethylene or polypropylene are converted to acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, and others. It is composed of resin such as acid-modified polyolefin resin, polyvinyl acetate resin, polyester resin, polystyrene resin, etc. modified with unsaturated carboxylic acid, etc., and these resins are formed into a film alone. Method or two or more resins A method of forming a multilayer co-extrusion film by using the above method, and a method of forming a film or a resin film by using two or more kinds of resins and mixing and forming the film before forming the film. Can be used. The film thickness of the heat-sealing base film is 5 to 5.
About 300 μm, more preferably about 10 to 100 μm is desirable.

In the above, when forming a stretched base film or a heat-sealing base film, for example, the processability, heat resistance, weather resistance, mechanical properties, dimensional stability, Oxidizing, slippery, mold release, flame retardant,
Various plastic compounding agents and additives can be added for the purpose of improving and modifying the antifungal property, electric properties, etc., and the amount of the additive can be from a very small amount to several tens%. They can be arbitrarily added according to the purpose.
Further, in the above, as a general additive, for example, a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a filler, a reinforcing agent, a reinforcing agent, an antistatic agent, a flame retardant, a flame retardant, a foaming agent, A fungicide, a pigment, and others can be used. In the present invention, as the stretched base film or the heat-sealing base film, if necessary, for example, corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas or nitrogen gas, or the like may be used. Pretreatment such as treatment, glow discharge treatment, oxidation treatment using a chemical agent, and the like can be optionally performed. The above-mentioned surface pretreatment may be performed in another step before forming the first or second barrier thin film mainly composed of an inorganic oxide by a plasma enhanced chemical vapor deposition method. In the case of surface treatment by glow discharge treatment or the like, pretreatment by in-line treatment can be performed as pretreatment for forming the first or second barrier thin film mainly composed of the above-mentioned inorganic oxide. In this case, there is an advantage that the manufacturing cost can be reduced. The above-mentioned surface pretreatment is a method for improving adhesion between a stretched base film or a heat-sealing base film and a first or second barrier thin film mainly composed of an inorganic oxide. As a method for improving the above-mentioned adhesion, for example, a primer coating agent may be previously applied to the surface of a stretched base film or a heat-sealing base film. A layer, an undercoat agent layer, a vapor-deposited anchor coat agent layer, or the like can be arbitrarily formed. As the coating agent layer for the above pretreatment, for example, a resin composition containing a polyester-based resin, a polyurethane-based resin, or the like as a main component of the vehicle can be used. In the above, as a method for forming the coating agent layer, for example, a coating agent such as a solvent type, an aqueous type, or an emulsion type is used, and a roll coating method, a gravure roll coating is used. The coating can be performed using a coating method such as a method, a kiss coating method, or the like.
As a post-process after biaxial stretching of the stretched base film, or in-line processing of biaxial stretching,
It can be carried out in a film forming step or the like.

Next, in the present invention, the first or second barrier thin film mainly composed of an inorganic oxide formed by the plasma chemical vapor deposition method, which constitutes the laminated material according to the present invention, will be described. Examples of the first or second barrier thin film mainly composed of an inorganic oxide include, for example, a stretched base film, and a heat-sealing film.
Chemical vapor deposition (CVD) such as low-temperature plasma-enhanced chemical vapor deposition using a low-temperature plasma generator or the like, using a monomer gas for vapor deposition of an organic silicon compound or the like as a raw material, It can be manufactured by a method of forming a vapor-deposited thin film of an inorganic oxide such as silicon oxide. In the above, as the low-temperature plasma generator, for example, a generator such as a high-frequency plasma, a pulse wave plasma, or a microwave plasma can be used. Thus, in the present invention, a highly active and stable plasma is obtained. For this purpose, it is desirable to use a generator using a high-frequency plasma method. Specifically, a method of forming the first and second barrier thin films mainly composed of an inorganic oxide by the low-temperature plasma chemical vapor deposition method will be described by way of an example. FIG. FIG. 2 is a schematic configuration diagram of a low-temperature plasma chemical vapor deposition apparatus showing an outline of a method for forming a first or second barrier thin film mainly composed of an inorganic oxide by a chemical vapor deposition method.

As shown in FIG. 3, in the present invention, the vacuum chamber-1 of the low-temperature plasma chemical vapor deposition apparatus 11 is used.
The stretched base film 2 or the heat-sealable base film 4 is unwound from the unwinding roll 13 disposed in the roll 2, and the stretched base film 2 or the heat-sealable base film 4 is further fed.
The sealable base film 4 is conveyed onto the peripheral surface of the cooling / electrode drum 15 at a predetermined speed via the auxiliary roll 14.
In the present invention, oxygen gas, an inert gas, a monomer gas for vapor deposition such as an organic silicon compound, and the like are supplied from the gas supply devices 16 and 17 and the raw material volatile supply device 18 and the like. The vacuum chamber-1 was passed through the raw material supply nozzle 19 while adjusting the gas mixture composition for vapor deposition.
2, the mixed gas composition for vapor deposition is introduced, and the stretched base film 2 or the heat-sealing base film 4 conveyed on the cooling / electrode drum 15 peripheral surface described above. Next, a plasma is generated by the glow discharge plasma 20 and irradiated with the plasma to form a deposited thin film of an inorganic oxide such as silicon oxide, thereby forming a film. In the present invention, at this time, a predetermined power is applied to the cooling / electrode drum 15 from a power source 21 disposed outside the chamber, and a magnet 22 is provided near the cooling / electrode drum 15.
And the generation of plasma is promoted,
The stretched base film 2 or the heat-sealing base film 4 on which the vapor-deposited thin film of the inorganic oxide such as silicon oxide has been formed as described above, is wound up through the auxiliary roll 23 and rolled up.
Then, the first or second barrier thin film mainly composed of an inorganic oxide can be manufactured by the low-temperature plasma chemical vapor deposition method according to the present invention. In the figure, reference numeral 25 denotes a vacuum pump. The above exemplification is merely an example, and it goes without saying that the present invention is not limited thereby.

In the above, a monomer for vapor deposition of an organic silicon compound or the like for forming a vapor deposited thin film of an inorganic oxide such as silicon oxide.
As the gas, for example, 1.1.3.3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, Phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, and the like can be used. In the present invention, among the organic silicon compounds as described above, the use of 1.1.3.3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material is advantageous in terms of handleability and formed deposited film. It is a particularly preferable raw material in view of its properties and the like. In the present invention, as the inert gas as a carrier gas, argon, helium, xenon, and others can be used.

In the present invention, in the case of the deposited silicon oxide thin film formed above, the deposited silicon oxide thin film is represented by the formula SiO _x (where X represents a number from 0 to 2). Is a continuous vapor-deposited thin film mainly composed of silicon oxide represented by the formula:
_X (where X represents a number from 1.3 to 1.9) is preferably a thin film mainly composed of a deposited silicon oxide film. In the above, the value of X changes depending on the molar ratio of the monomer gas to the oxygen gas, the energy of the plasma, and the like. In general, as the value of X decreases, the gas permeability decreases, but the value of the film itself increases. It has a yellow color and poor transparency. Further, the deposited thin film of silicon oxide as the first or second barrier thin film has silicon (Si) and oxygen (O) as essential constituent elements, and further has carbon (C).
And hydrogen (H) are formed of a deposited film of silicon oxide containing one or both elements as trace constituent elements, and the thickness thereof is in the range of 50 ° to 500 °. The constituent ratio between the essential constituent elements and the trace constituent elements changes continuously in the film thickness direction. Further, when the silicon oxide vapor-deposited thin film as the first or second barrier thin film contains a compound made of carbon, the carbon content decreases in the depth direction of the film thickness. It is characterized by the following.

Thus, in the present invention, the above-mentioned first or second barrier thin film of the deposited silicon oxide thin film is, for example, an X-ray photoelectron spectrometer (Xray Ph.
otoelectron Spectroscopy,
XPS), secondary ion mass spectrometer (Secondar)
y Ion Mass Spectroscopy, S
Confirming the physical properties as described above by performing elemental analysis of the deposited silicon oxide thin film using a method of performing ion etching in the depth direction or the like using a surface analyzer such as IMS). Can be done. In the present invention, the thickness of the deposited silicon oxide thin film as the first or second barrier thin film is desirably 500 ° or less, and specifically, the thickness is , 50-500 °, more preferably 100-30
0 ° is desirable, so in the above, 300 °,
Further, when the thickness is more than 500 °, cracks and the like are easily generated in the film, which is not preferable.
Further, if it is less than 50 °, it is difficult to exhibit the effect of the barrier property, which is not preferable. In the above description, the film thickness can be measured by a fundamental parameter method using, for example, a fluorescent X-ray analyzer (model name: RIX2000) manufactured by Rigaku Corporation. Further, in the above, the first or the second
Means for changing the thickness of the deposited thin film of silicon oxide as a barrier thin film is to increase the deposition rate of the deposited film, that is, to increase the amount of the monomer gas and the oxygen gas or to reduce the deposition rate. It can be performed by a method or the like. In addition, when forming a thin film of an inorganic oxide by a low-temperature plasma chemical vapor deposition method on a substrate having poor heat resistance, such as the above-mentioned stretched substrate film, or a heat-sealing substrate film, If the deposition rate is reduced, the exposure time to plasma becomes longer and the film or the like deteriorates, which is not preferable. In general, it is preferable to form the deposition film at a deposition rate of 50 to 200 m / min.

Accordingly, the first film formed as described above is formed.
Alternatively, a deposited thin film of silicon oxide as the second barrier thin film
Oxygen permeation at 23 ° C and 90% relative humidity
The coefficient is 1.0 × 10^-15cm^Three(STP) cm / c
m^Two· Sec · cmHg or less. The first or above
Is the acid of the deposited thin film of silicon oxide as the second barrier thin film
The elemental transmission coefficient can be calculated by the following method. First, the stretching base
Material film or heat-sealing base film
Film thickness L ₁, The stretched base film, or
-The oxygen permeability coefficient of the base film₁, Low temperature plasm
1st or 2nd based on inorganic oxides by chemical vapor deposition
Represents the thickness of the second barrier thin film as L_Two, The low temperature plasma
1st or 2nd mainly composed of inorganic oxide by chemical vapor deposition
The oxygen permeability coefficient of the barrier thin film of No. 2 is P_Two, Stretched base material
Heat-sealable base film and low-temperature
No. 1 mainly composed of inorganic oxide by plasma enhanced chemical vapor deposition
Or the film thickness of the second base film and the stretched base film.
Film or heat-sealing base film and low temperature
The first mainly composed of inorganic oxides by plasma-enhanced chemical vapor deposition
Alternatively, let P be the oxygen permeability coefficient with the second barrier thin film.
Then, low-temperature plasma-enhanced chemical vapor deposition
Or second barrier properties mainly composed of inorganic oxides
Oxygen permeability coefficient of thin film [cm^Three(STP) cm / cm^Two
.Sec.cmHg] can be calculated. L / P = L₁/ P₁+ L_Two/ P_Two─────1 formula

The above equation (1) can be converted into the following equation (2). 1 / (P / L) = 1 / (P 1 / L 1) + 1 / (P 2 / L 2) ─────2 formula Incidentally, the two equations shown above _{P / L, P 1 / L} 1 , P ₂
/ L ₂ is a stretched substrate film or
Oxygen permeability between stretchable base film and first or second barrier thin film mainly composed of inorganic oxide by low temperature plasma chemical vapor deposition, stretched base film, or heat sealable base film Oxygen permeability of the material film and the first, mainly composed of inorganic oxides by low temperature plasma chemical vapor deposition
Alternatively, it indicates the oxygen permeability of the second barrier thin film,
An oxygen permeability coefficient of the stretched base film or the heat-sealing base film and the first or second barrier thin film mainly composed of an inorganic oxide formed by low-temperature plasma-enhanced chemical vapor deposition; Film or heather
The oxygen permeability coefficient of the base material film was measured, and the first material mainly composed of an inorganic oxide was formed by low-temperature plasma chemical vapor deposition.
Alternatively, by multiplying the oxygen permeability of the second barrier thin film by the thickness of the first or second barrier thin film mainly composed of an inorganic oxide by low temperature plasma chemical vapor deposition, the desired low temperature plasma chemical vapor deposition The oxygen permeability coefficient of the first or second barrier thin film mainly composed of an inorganic oxide can be calculated. In the above description, the oxygen permeability is measured, for example, using an oxygen permeability meter [model name, OX-TRAN 2/2] manufactured by MOCON, USA.
0] under the conditions of 23 ° C. and 90% RH. The film thickness can be measured using, for example, a fluorescent X-ray analyzer (model RIX2000, manufactured by Rigaku Corporation). , Can be measured by the fundamental parameter method.

Next, in the present invention, the stretched base film and the heat-sealing base film are laminated with the first and second barrier thin films facing each other. As a method, for example, a dry lamination method of laminating via a laminating adhesive layer with a laminating adhesive, or an extruding laminating method of laminating via a melt extruded resin layer with a melt extruded adhesive resin. It can be performed by a method such as In the above, as the adhesive for laminating, for example, a one-part or two-part curing or non-curing type vinyl, (meth) acrylic, polyamide, polyester, polyether,
Adhesives for laminating such as solvent type, aqueous type or emulsion type such as polyurethane type, epoxy type, rubber type and the like can be used. Examples of the coating method of the adhesive for laminating include, for example, a direct gravure roll coating method and a gravure roll coating method.
Coating method, kiss coating method, reverse roll coating method, Fonten method, transfer roll coating method and the like can be applied. 1 to 10 g / m ² (dry state) position, more preferably, 1 to 5 g / m ² (dry state) position is desirable. In the present invention, for example, an adhesion promoter such as a silane coupling agent can be arbitrarily added to the adhesive for laminating.

Next, in the above, as the melt-extruded adhesive resin, the resin forming the heat-sealing base film described above can be used in the same manner. Thus, in the present invention, as the melt-extruded adhesive resin, it is particularly preferable to use low-density polyethylene, furthermore, linear (linear) low-density polyethylene and acid-modified polyethylene. The thickness of the melt-extruded resin layer of the melt-extruded adhesive resin is 5 to
About 100 μm, more preferably about 10 to 50 μm is desirable. In the present invention, when it is necessary to obtain a stronger adhesive strength when performing the above-mentioned lamination, if necessary, for example, an anchor may be provided on the first barrier thin film surface.
An adhesion improver such as a coating agent may be coated.
As the above-mentioned anchor coating agent, specifically, for example, an organic titanium-based anchor coating such as alkyl titanate is used.
Water-based or oil-based anchor-coating agents, such as a coating agent, an isocyanate-based anchor-coating agent, a polyethyleneimine-based anchor-coating agent, a polybutadiene-based anchor-coating agent, and the like. Can be used. Thus, in the present invention, the above-mentioned anchor coating agent can be used, for example, by roll coating, gravure coating, knife coating, dip coating, spray coating, and other coating methods. In-
And dry the solvent, diluent, etc.
The agent layer can be formed. In the above, the coating amount of the anchor coating agent is preferably about 0.1 to 5 g / m ² (dry state).

Next, in the present invention, as a print pattern layer constituting the laminate according to the present invention, for example, a usual gravure ink composition, offset ink composition Products, letterpress ink compositions, screen ink compositions, and other ink compositions, for example, gravure printing, offset printing,
Use letterpress printing method, silk screen printing method, other printing methods such as characters, figures, pictures, symbols,
It can be formed by forming a desired printed pattern layer made of other materials. Alternatively, a desired print pattern layer is formed on a resin film or the like in advance by using the ink composition in the same manner as described above and by a normal printing method. The printed picture layer can also be formed by laminating on a thin film. Thus, in the present invention, since the first barrier thin film mainly composed of an inorganic oxide formed by the plasma chemical vapor deposition method contains carbon in the film, for example, a physical vapor deposition method such as a vacuum vapor deposition method is used. The wettability is lower than that of the deposited inorganic oxide thin film. Therefore, the surface is oxidized by corona discharge treatment, ozone treatment, low-temperature plasma treatment with oxygen gas or nitrogen gas, glow discharge treatment, chemical treatment, etc. It can also be processed. The above-mentioned surface treatment may be performed in a separate step after forming the first barrier thin film.
In-line processing as a post-treatment of the plasma enhanced chemical vapor deposition method is advantageous in terms of manufacturing cost. Further, in the present invention, a printed pattern layer or the like may be formed on the surface of the first barrier thin film after previously coating an Insatsu primer or the like.

In the above, various ink compositions include, for example, polyolefin resins such as polyethylene resins and chlorinated polypropylene resins, and poly (meth) acrylic resins as vehicles constituting the ink compositions. Resin, polyvinyl chloride resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate copolymer, polystyrene resin, styrene-butadiene copolymer, vinylidene fluoride resin, polyvinyl alcohol resin, polyvinyl acetate Resin, polyvinyl butyral resin, polybutadiene resin, polyester resin, polyamide resin, alkyd resin, epoxy resin, unsaturated polyester resin, thermosetting poly (meth) acrylic resin, Melamine resin, urea resin, polyurethane resin, phenol resin, Silene-based resin, maleic acid resin, nitrocellulose, ethylcellulose, acetylbutylcellulose, ethyloxyethylcellulose, and other fibrous resins, chlorinated rubber, cyclized rubber, and other rubber-based resins, and petroleum-based resins , Rosin, casein and other natural resins, linseed oil, soybean oils and other fats and oils, and one or more other resin mixtures can be used. Thus, in the present invention, one or more of the above-mentioned vehicles are used as a main component, and one or more of colorants such as dyes and pigments are added thereto. , For example, fillers,
Optionally add additives such as stabilizers, plasticizers, antioxidants, light stabilizers such as ultraviolet absorbers, dispersants, thickeners, drying agents, lubricants, antistatic agents, crosslinking agents, etc. It is possible to use ink compositions in various forms which are sufficiently kneaded with a diluent or the like.

The oxygen permeability of the laminate according to the present invention produced as described above is a temperature of 23 ° C. and a relative humidity of 90% R
In H, it is 5 cc / m ² · day · atm or less. The above-mentioned measurement of oxygen permeability is performed at 23 ° C. and 90% using, for example, the above-described oxygen permeability measurement device (model name, OX-TRAN 2/20) manufactured by MOCON, USA. It can be measured under RH conditions.

In general, a packaging container is subjected to severe physical and chemical conditions, so that the packaging material constituting the packaging container is required to have strict packaging suitability, and to have a deformation prevention strength. , Drop impact strength, pinhole resistance, heat resistance,
Various conditions such as sealing property, quality maintenance property, workability, hygiene property, etc. are required. For this reason, in the present invention, when producing the laminated material according to the present invention, further, A material that satisfies the above conditions can be arbitrarily selected and laminated to produce a laminated material. Specifically, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid Ethyl copolymer, ethylene-acrylic acid or methacrylic acid copolymer, methylpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer Coalescing, poly (meth) acrylic resin, polyacrylonitrile resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, Polyamide resin, polycarbonate Ne - DOO resins, polyvinyl alcohol - Le resins, ethylene - saponified vinyl acetate copolymer, fluorine resin,
It can be arbitrarily selected from known resin films or sheets such as diene resins, polyacetal resins, polyurethane resins, nitrocellulose and others. In addition, for example, a film such as cellophane, synthetic paper, or the like can be used. In the present invention, the above-mentioned film or sheet may be any of unstretched and uniaxially or biaxially stretched. The thickness is arbitrary, but is from several μm to 3 μm.
It can be used by selecting from a range of about 00 μm.
Further, in the present invention, the film or sheet may be any film such as an extruded film, an inflation film, or a coating film.

Next, in the present invention, a method for producing a packaging container having various forms by carrying out bag making or box making using the laminated material according to the present invention will be described. Using the laminated material produced above,
The heat-sealing base film of the inner layer is opposed to the surface, and it is folded or the two sheets are overlapped, and the peripheral edge is heat-sealed to form a seal portion. Can be provided to form a bag. Thus, as a bag-making method, the above-mentioned laminated material is bent with its inner layer facing the surface, or two of them are overlapped, and the peripheral end of the outer periphery is further sealed with, for example, a side sheet. Seal type, two-way seal type, three-way seal type, four-way seal type, envelope-attached seal type, gasket-attached seal type (pyro-seal type), pleated seal
The heat-sealing method of the present invention can be used to manufacture various types of packaging containers according to the present invention by heat-sealing such as a heat seal type, a flat bottom seal type, a square bottom seal type, etc. it can. In addition, for example, a self-supporting packaging bag (standing pouch) and the like can be manufactured. In the present invention, a tube container and the like can be manufactured using the above-described composite film. In the above, as a method of heat sealing, for example, a bar seal, a rotating roll seal,
It can be carried out by a known method such as a belt seal, an impulse seal, a high-frequency seal, an ultrasonic seal, and the like. In the present invention, a spout such as a one-piece type, a two-piece type, etc., or a zipper for opening and closing can be arbitrarily attached to the packaging container as described above.

Thus, in the present invention, packaging containers of various forms formed by bag making or box making using the laminated material according to the present invention are mainly composed of inorganic oxides formed by plasma chemical vapor deposition. The first and second barrier thin films are rich in bending resistance and excellent in impact resistance. For example, the first and second barrier thin films are used in post-processing such as laminating, printing, bag making or box making. And the occurrence of cracks and the like in the second barrier thin film is not recognized, oxygen gas, gas barrier properties against water vapor gas, etc., especially excellent in oxygen gas barrier properties, also has transparency, excellent visibility, for example, It has excellent filling and packaging suitability and preservation suitability for various articles such as foods and drinks, pharmaceuticals, detergents, shampoos, oils, toothpastes, chemicals and cosmetics such as adhesives and adhesives, and others.

[0028]

The present invention will be described more specifically with reference to the following examples. Example 1 (1). A 20 μm thick biaxially stretched polypropylene film (OPP, manufactured by Nimura Chemical Industry Co., Ltd., trade name, FOK, one-sided corona treated product) was used as a substrate, and this was fed to a low-temperature plasma chemical vapor deposition apparatus. Then, a deposited silicon oxide film having a thickness of 120 ° was formed on one surface of the biaxially stretched polypropylene film under the following conditions. (Evaporation conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 10: 10 (unit: slm) Degree of vacuum in vacuum chamber: 5.5 × 10 ⁻⁶ mbar In evaporation chamber Degree of vacuum: 6.5 × 10 ^-2 mbar Cooling / electrode drum supply power: 18 kW Film transfer speed: 80 m / min Evaporation surface: Corona treated surface Next, biaxially oriented polypropylene on which a silicon oxide evaporated thin film was formed as described above Corona treatment was performed on the surface of the deposited silicon oxide thin film under the following conditions. As a result, the surface tension of the surface of the deposited silicon oxide thin film was 35 dyn to 62 dyn.
Improved. Output: 10 kw Processing speed: 100 m / min (2). As a substrate, a 60 μm-thick unstretched polypropylene film (CPP, manufactured by Toyobo Co., Ltd., trade name, P
1120, a single-sided corona-treated product) was mounted on a delivery roll of a low-temperature plasma-enhanced chemical vapor deposition apparatus, and a deposited silicon oxide thin film having a thickness of 100 ° was formed on the above unstretched polypropylene film under the following conditions. Formed on one side. (Evaporation conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 7: 7 (unit: slm) Degree of vacuum in vacuum chamber: 5.0 × 10 ⁻⁶ mbar In evaporation chamber Degree of vacuum: 6.0 × 10 ^-2 mbar Cooling / electrode drum power supply: 13 kW Film transport speed: 80 m / min Evaporation surface: Corona treated surface Next, a non-stretched polypropylene film on which a silicon oxide evaporated thin film was formed as described above Corona treatment was performed on the surface of the silicon oxide vapor-deposited thin film in the same manner as described above to form a corona-treated surface. (3). Next, after forming a desired print pattern layer on the corona-treated surface of the silicon oxide vapor-deposited thin film of the biaxially stretched polypropylene film using a gravure printing machine, the biaxially stretched polypropylene film is dried by a dry laminating machine. Attached to the first delivery roll, and the gravure roll
A two-component curable polyurethane-based laminating adhesive using a coating method (manufactured by Takeda Pharmaceutical Co., Ltd., A-5
15, hardener, A-50, solvent, ethyl acetate) to 3.0
g / m ² (dry weight) to form a laminating adhesive layer. Subsequently, the corona-treated surface of the deposited silicon oxide thin film of the unstretched polypropylene film is opposed to the laminating adhesive layer surface, and the biaxially stretched polypropylene film and the unstretched polypropylene film are laminated. A laminated material according to the present invention having the following layer constitution was produced. 20 μm thick biaxially oriented polypropylene film, evaporated silicon oxide thin film / printed picture layer /
Adhesive layer for laminating / Deposited thin film of silicon oxide, thickness 60
μm unstretched polypropylene film

Example 2 In Example 1 described above, ethylene-
Use methacrylate (EMAA) resin, thickness 25μ
m and laminated by a melt extrusion laminating method. Except for the above, a laminated material according to the present invention having the following layer constitution was produced in exactly the same manner as in Example 1 described above. Biaxially oriented polypropylene film with a thickness of 20 μm, deposited silicon oxide thin film / printed picture layer / melt extruded resin layer / silicon oxide deposited thin film, non-oriented polypropylene film with a thickness of 60 μm

Embodiment 3 (1). As a base material, a 12 μm-thick biaxially stretched polyethylene terephthalate film (PET, manufactured by Toyobo Co., Ltd., trade name, E5100, one-sided corona treated product) is used, and is fed to a low-temperature plasma chemical vapor deposition apparatus A 180 ° -thick silicon oxide vapor-deposited thin film was formed on one surface of the above biaxially stretched polyethylene terephthalate film under the following conditions. (Evaporation conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 3: 3 (unit: slm) Degree of vacuum in vacuum chamber: 5.5 × 10 ⁻⁶ mbar In evaporation chamber Degree of vacuum: 6.5 × 10 ^-2 mbar Cooling / electrode drum supply power: 18 kW Film transfer speed: 110 m / min Evaporation surface: Corona treated surface Next, biaxially stretched polyethylene on which a silicon oxide evaporated thin film was formed as described above The surface of the silicon oxide vapor-deposited thin film of the terephthalate film was subjected to corona treatment under the following conditions. As a result, the surface tension of the surface of the deposited silicon oxide thin film was 35 dyn.
To 62 dyn. Output: 10 kw Processing speed: 100 m / min (2). On the other hand, a linear low-density polyethylene film (LLDPE, manufactured by Tamapoly Co., Ltd., trade name, UB-1, single-sided corona-treated product) having a thickness of 60 μm was used as a substrate, and this was used as a low-temperature plasma chemical vapor deposition apparatus. And a 90 ° -thick deposited silicon oxide thin film was formed on one surface of the linear low-density polyethylene film under the following conditions. (Evaporation conditions) Reaction gas mixing ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 10: 8 (unit: slm) Degree of vacuum in vacuum chamber: 5.5 × 10 ⁻⁶ mbar In evaporation chamber Degree of vacuum: 6.5 × 10 ^-2 mbar Cooling / electrode drum power supply: 12 kW Film transport speed: 70 m / min Evaporation surface: Corona treated surface On the surface of the vapor-deposited thin film of silicon oxide of the density polyethylene film,
Corona treatment was performed in the same manner as above to form a corona treated surface. (3). Next, on the corona-treated surface of the deposited silicon oxide thin film of the biaxially stretched polyethylene terephthalate film,
After forming a desired print pattern layer using a gravure printing machine, the biaxially stretched polyethylene terephthalate film is mounted on a first delivery roll of a dry laminating machine, and a gravure roll coat is formed on the print pattern layer surface. 2 using the
Liquid-curable polyurethane laminating adhesive (manufactured by Takeda Pharmaceutical Co., Ltd., main agent, A-515, curing agent, A-5
0, solvent, ethyl acetate) to 3.0 g / m ² (dry weight)
To form a laminating adhesive layer.
Next, the corona-treated surface of the vapor-deposited thin film of silicon oxide of the linear low-density polyethylene film is opposed to the surface of the adhesive layer for laminating, and the linear-density polyethylene terephthalate film is linearized By laminating with a low-density polyethylene film, a laminated material according to the present invention having the following layer constitution was produced. Biaxially stretched polyethylene terephthalate film with a thickness of 20 μm, evaporated thin film of silicon oxide /
Printed pattern layer / Laminate adhesive layer / Evaporated thin film of silicon oxide, linear low-density polyethylene film with a thickness of 60 μm

Example 4 In Example 3, a low-density polyethylene resin was used as a laminating method, and was melt-extruded to a thickness of 20 μm and laminated by a melt-extrusion laminating method. A laminated material according to the present invention having the following layer constitution was produced in exactly the same manner as in Example 3. Thickness 20μm
Biaxially stretched polyethylene terephthalate film, silicon oxide vapor deposited thin film / printed picture layer / melt extruded resin layer / silicon oxide vapor deposited thin film, 60 μm thick linear low density polyethylene film

Embodiment 5 (1). First, a 15 μm-thick biaxially stretched polyamide film (ONy, manufactured by Toyobo Co., Ltd., trade name, N4140, one-sided corona-treated product) was used as a substrate, and this was fed to a low-temperature plasma chemical vapor deposition apparatus. Then, a deposited silicon oxide thin film having a thickness of 170 ° was formed on one surface of the above-mentioned biaxially stretched polyamide film under the following conditions. (Evaporation conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 3: 3 (unit: slm) Degree of vacuum in vacuum chamber: 5.5 × 10 ⁻⁶ mbar In evaporation chamber Degree of vacuum: 6.5 × 10 ^-2 mbar Cooling / electrode drum supply power: 18 kW Film transfer speed: 110 m / min Evaporation surface: Corona treated surface Next, biaxially stretched polyamide on which a silicon oxide evaporated thin film was formed as described above Corona treatment was performed on the surface of the deposited silicon oxide thin film under the following conditions. As a result, the surface tension of the surface of the deposited silicon oxide thin film was improved from 35 dyn to 62 dyn. Output: 10 kw Processing speed: 100 m / min (2). Next, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm (manufactured by Toyobo Co., Ltd., trade name, E
5100, a single-sided corona-treated product), a desired printed picture layer is formed on the corona-treated surface using a gravure printing machine, and then the above-mentioned biaxially oriented polyethylene terephthalate film and biaxially oriented polyamide film With the printed pattern layer surface and the biaxially stretched polyamide film surface facing each other, a two-component curable polyurethane-based laminating adhesive (manufactured by Takeda Pharmaceutical Co., Ltd., main agent, A-515, curing agent, A-50, solvent, ethyl acetate)
/ M ² (dry weight) via a laminating adhesive layer coated at a ratio of ² to produce a laminate. (3). Next, after laminating the biaxially stretched polyethylene terephthalate film and the biaxially stretched polyamide film as described above, the laminate is mounted on a first delivery roll of a dry laminating machine, and the biaxially stretched polyamide A two-component curable polyurethane-based laminating adhesive (manufactured by Takeda Pharmaceutical Co., Ltd., A-51) is applied to the corona-treated surface of the deposited silicon oxide thin film using a gravure roll coating method.
5, curing agent, A-50, solvent, ethyl acetate) 3.0 g
/ M ² (dry weight) to form a laminating adhesive layer. Then, the corona-treated surface of the vapor-deposited thin film of silicon oxide of the unstretched polypropylene film produced in Example 1 was opposed to the laminating adhesive layer surface, and the laminate and the unstretched polypropylene film were combined. By laminating, a laminated material according to the present invention having the following layer constitution was produced. 12 μm thick biaxially stretched polyethylene terephthalate film / printed picture layer / laminate adhesive layer / 15 μm thick biaxially stretched polyamide film / silicon oxide vapor deposited thin film / laminate adhesive layer / oxidation Evaporated thin film of silicon, non-stretched polypropylene film with a thickness of 60 μm

Comparative Example 1 In Example 1, the heat-sealable base material film had a thickness of 60 with no deposited silicon oxide thin film.
A laminated material having the following layer structure was produced in the same manner as in Example 1 except that a non-stretched polypropylene film of μm was used. Biaxially oriented polypropylene film with a thickness of 20 μm, evaporated thin film of silicon oxide / printed picture layer / adhesive layer for laminating / unstretched polypropylene film with a thickness of 60 μm

Comparative Example 2 In Example 1 above, a biaxially oriented polypropylene film having a thickness of 20 μm on which no silicon oxide vapor-deposited thin film was formed was used as the stretched base film. In the same manner as in Example 1, a laminated material having the following layer structure was produced. Biaxially oriented polypropylene film with a thickness of 20 μm / printing pattern layer / adhesive layer for laminating / vapor-deposited thin film of silicon oxide, non-oriented polypropylene film with a thickness of 60 μm

COMPARATIVE EXAMPLE 3 In the above-mentioned Example 2, the heat-sealable base material film had a thickness of 60 with no deposited silicon oxide thin film.
A laminated material having the following layer structure was produced in the same manner as in Example 2 except that a non-stretched polypropylene film of μm was used. Biaxially oriented polypropylene film with a thickness of 20 μm, evaporated thin film of silicon oxide / printed picture layer / melt extruded resin layer / non-oriented polypropylene film with a thickness of 60 μm

Comparative Example 4 In Example 2, a biaxially stretched polypropylene film having a thickness of 20 μm on which no silicon oxide vapor-deposited thin film was formed was used as the stretched base film. In the same manner as in Example 2, a laminated material having the following layer structure was produced. 20 μm thick biaxially oriented polypropylene film / printed picture layer / melt extruded resin layer / vapor-deposited thin film of silicon oxide ・ 60 μm thick non-oriented polypropylene film

COMPARATIVE EXAMPLE 5 In the above-mentioned Example 3, the heat-sealable base material film had a thickness of 60 with no deposited silicon oxide thin film.
A laminated material having the following layer structure was produced in the same manner as in Example 3 except that a μm linear low-density polyethylene film was used. Biaxially stretched polyethylene terephthalate film with a thickness of 12 μm, deposited silicon oxide thin film / printed picture layer / laminate adhesive layer / thickness 60
μm linear low density polyethylene film

Comparative Example 6 In Example 3 above, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, on which no deposited silicon oxide film was formed, was used as the stretched base film. In the same manner as in Example 3, a laminated material having the following layer structure was manufactured. 12 μm thick biaxially stretched polyethylene terephthalate film / printed picture layer /
Adhesive layer for laminating / Deposited thin film of silicon oxide, thickness 60
μm linear low density polyethylene film

COMPARATIVE EXAMPLE 7 In Example 4, the heat-sealable base material film had a thickness of 60 with no silicon oxide deposited thin film.
A laminated material having the following layer structure was produced in the same manner as in Example 4 except that a μm linear low-density polyethylene film was used. Biaxially stretched polyethylene terephthalate film with a thickness of 12 µm, evaporated thin film of silicon oxide / printed picture layer / melt-extruded resin layer / thickness 60 µ
m linear low density polyethylene film

Comparative Example 8 In Example 4, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm on which no silicon oxide vapor-deposited film was formed was used as the stretched base film. In the same manner as in Example 4, a laminated material having the following layer constitution was manufactured. 12 μm thick biaxially stretched polyethylene terephthalate film / printed picture layer /
Melt extruded resin layer / Vacuum thin film of silicon oxide, thickness 60μ
m linear low density polyethylene film

Comparative Example 9 In Example 5, the heat-sealable base material film had a thickness of 60 with no silicon oxide deposited thin film.
A laminated material having the following layer configuration was produced in the same manner as in Example 5 except that a non-stretched polypropylene film of μm was used. 12 μm thick biaxially oriented polyethylene terephthalate film / printed picture layer / laminate adhesive layer / 15 μm thick biaxially oriented polyamide film / silicon oxide vapor deposited thin film / laminate adhesive layer / thickness 60μm unstretched polypropylene film

Comparative Example 10 In Example 5, a biaxially stretched polyamide film having a thickness of 15 μm on which a thin film of silicon oxide was not formed was used as a stretched base film. In the same manner as in Example 5, a laminated material having the following layer constitution was produced. 12 μm thick biaxially stretched polyethylene terephthalate film / printed picture layer / laminate adhesive layer / 15 μm thick biaxially stretched polyamide film / laminate adhesive layer / silicon oxide deposited thin film / thickness 60μ
m unstretched polypropylene film

Experimental Example 1 The oxygen permeability and water vapor permeability of each laminated material produced in Examples 1 to 5 and Comparative Examples 1 to 10 were measured. And Comparative Examples 1-1
Each of the laminated materials manufactured in Example No. 0 was bent 10 times using a gelboflex tester, and then the oxygen permeability and the water vapor permeability were measured in the same manner. (1). Measurement of Oxygen Permeability This is a condition of 23 ° C. and 90% RH in the United States.
The measurement was carried out using a measuring instrument (model name, OXTRAN) manufactured by MOCON. (2). Measurement of water vapor transmission rate This is a condition of temperature of 40 ° C and humidity of 90% RH in the United States,
The measurement was carried out using a measuring instrument (model name, PERMATRAN) manufactured by MOCON. The above measurement results are shown in Table 1 below. In Table 1, the unit of oxygen permeability is [cm ³ / m ² · day · atm].
The unit of the water vapor permeability is [g / m ² · d
ay.atm].

[0044]

From the results shown in Table 1 above, Examples 1 to 5
The laminate according to Comparative Example 1 was remarkably excellent in gas barrier properties against oxygen gas, water vapor gas, and the like, as compared with the laminates according to Comparative Examples 1 to 10. Further, even after bending, the laminated materials according to Examples 1 to 5 maintain the effect of gas barrier properties against oxygen gas, water vapor, and the like as they are, as compared with the laminated materials according to Comparative Examples 1 to 10. It was a clear confirmation that the flexibility was significantly improved. That is, in the present invention, the first and second barrier thin films mainly composed of an inorganic oxide formed by a plasma-enhanced chemical vapor deposition method are laminated while facing each other,
It has been clarified that the bending resistance, which is a characteristic of the thin film deposited by the plasma chemical vapor deposition method, is further improved.

EXPERIMENTAL EXAMPLE 2 A stretched base film and a heat-sealing base film each having a silicon oxide vapor-deposited thin film according to Examples 1 to 5 based on the above-described formulas 1 and 2. , The oxygen permeability coefficient was calculated. The results are shown in Table 2 below.

[0047] ┘

From the results shown in Table 2 above, Examples 1 and 2
And OPP, CPP, LLDP according to Examples 3 and 4
The oxygen permeability of the barrier thin film formed on the polyolefin resin film such as E is 1 × 10 ⁻¹⁵ or less, and the oxygen permeation of the barrier thin film formed on the PET or ONy film according to Examples 3 and 5. The coefficient was 1 × 10 ⁻¹⁶ or less. As a result, the barrier thin film formed on the polyolefin-based resin film is different in the adhesion and the film structure in the process of depositing the film from those of the barrier thin film formed on the film of PET, ONy, etc. This is considered to be due to the difference in the heat resistance of the plastic film as the base film.

[0049]

As is apparent from the above description, the present invention focuses on a vapor-deposited film having excellent bending resistance by a plasma enhanced chemical vapor deposition method. A first barrier thin film mainly composed of an inorganic oxide formed by a method is provided, and a second film mainly composed of an inorganic oxide formed by a plasma-enhanced chemical vapor deposition method is provided on one surface of a heat-sealing base film. A barrier thin film is provided, and the stretched base film and the heat-sealing base film are placed on the first barrier thin film and the second barrier film. A laminate is manufactured by laminating through an adhesive layer for laminating by a laminating method or a thermoplastic resin layer extruded by a laminating method by an extruding laminating method. , Making this into a bag or a box to make a packaging container , The 該包 wearing vessel, for example,
Filling and packaging various products such as food and drink, pharmaceuticals, chemicals, daily necessities, sundries, etc.
And the second barrier thin film has bending resistance and the like, and is excellent in flexibility and the like, and the first and second barrier thin films have cracks or the like during lamination, and further, during bag making or box making. No occurrence of lamination was observed, and it had excellent laminating suitability, suitability for bag making, etc., and as a result, gas barrier properties against oxygen gas, water vapor, etc., particularly, excellent gas barrier properties against oxygen gas, alteration of contents, Prevents modification, etc. and has stable long-term distribution and storage suitability, and is excellent in transparency, so that the contents can be visually recognized from the outside and extremely excellent and good packaging That is, it is possible to produce a useful laminate that can be produced at low cost. That is, the present invention provides a gas barrier property against oxygen gas, water vapor gas, and the like by stacking a first barrier thin film mainly composed of an inorganic oxide and a second barrier thin film facing each other by plasma enhanced chemical vapor deposition. Is significantly improved, and furthermore, the effect can be further enhanced by the bending resistance of the thin film deposited by the plasma enhanced chemical vapor deposition method.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view schematically showing a layer configuration of an example of a laminated material according to the present invention.

FIG. 2 is a schematic cross-sectional view schematically showing a layer configuration of another example of the laminated material according to the present invention.

FIG. 3 shows first and second barriers mainly composed of an inorganic oxide formed by a low-temperature plasma-enhanced chemical vapor deposition method on one surface of a stretched base film and a heat-sealing base film according to the present invention. FIG. 1 is a schematic configuration diagram of a low-temperature plasma chemical vapor deposition apparatus showing an outline of a method for forming a conductive thin film.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Laminated material 1a Laminated material 2 Stretched base film 3 First barrier thin film 3a Second barrier thin film 4 Heat seal base film 5 Laminate adhesive layer 5a Melt extruded resin layer 6 Printing Picture layer

Continued on the front page F-term (reference) 3E086 AD01 BA04 BA15 BA24 BA40 BB01 BB22 BB51 BB87 CA01 CA11 CA28 CA35 4F100 AA17B AA17D AA20 AA20B AA20D AH06B AH06D AK01E AK06 AK07 AK25 BA10 E23 BA04 BA05 E02 EH66B EH66D EJ37A EJ38 EJ55 EJ61 EJ61B EJ61D EJ65E GB15 GB23 HB31E HB35 JA20B JA20D JD03 JD03B JD03D JD04 JK13 JK17 JL02 JL12C JN01 YY00 YY00B YY00D

Claims (6)

[Claims] 1. A first barrier thin film mainly composed of an inorganic oxide formed by a plasma-enhanced chemical vapor deposition method is provided on one surface of a stretched base film, and one of a heat-sealing base film is provided on the other side. A second barrier thin film mainly composed of an inorganic oxide formed by a plasma enhanced chemical vapor deposition method is provided on the surface, and the above-mentioned stretched base film and heat-sealing base film are combined with the first barrier thin film. The laminating film is laminated with a laminating adhesive layer formed by a dry laminating method or a melt extruded resin layer formed by an extruding laminating method, with the conductive thin film surface and the second barrier film surface facing each other. A laminated material characterized in that: 2. A method according to claim 1, wherein the first barrier thin film is directly or through a primer agent layer formed by a printing primer agent.
The laminated material according to claim 1, wherein a printed pattern layer is provided. 3. The laminate according to claim 1, wherein the first and second barrier thin films are made of a barrier thin film mainly composed of silicon oxide formed by a plasma enhanced chemical vapor deposition method. 4. The first and second barrier thin films have silicon (Si) and oxygen (O) as essential constituent elements, and further have one of carbon (C) and hydrogen (H), or ,
It is composed of a vapor-deposited thin film of silicon oxide containing both elements as trace constituent elements, and has a thickness of 50 ° to 50 °.
4. The laminate according to claim 3, wherein the thickness is in the range of 0 [deg.], And the composition ratio of the essential constituent element and the trace constituent element changes continuously in the film thickness direction. 5. The method according to claim 1, wherein one of the first and second barrier thin films has an oxygen permeability coefficient of 1.0 × 10 ⁻¹⁵ cm ³ (STP) · cm / cm at a temperature of 23 ° C. and a relative humidity of 90%. ^Two
The laminate according to any one of claims 1 to 4, wherein the laminate is not more than -sec-cmHg. 6. The laminate has an oxygen permeability of 5 cc / m ² · day · a at a temperature of 23 ° C. and a relative humidity of 90% RH.
The laminated material according to any one of claims 1 to 5, wherein the thickness is not more than tm.