JP2000085049A - Laminated material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a low-priced laminated material which uses a biaxially oriented polypropylene film as a base material film and shows outstanding gas barrier properties to an oxygen gas and water vapor, and also is highly transparent and pliable. SOLUTION: This laminated material comprises a first thin film 3 with barrier properties composed mainly of an inorganic oxide formed by a low temperature plasma chemical vapor deposition process on one of the faces of a biaxially oriented polypropylene film 2 and further a multilayer laminated film 7 consisting of at least a thermoplastic resin layer 4, a second resin layer 5 with barrier properties and a thermoplastic resin layer 4 laminated by a co-extrusion lamination process to the face of the first thin film 3 with barrier properties.

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 an inexpensive laminated material having excellent gas barrier properties against oxygen gas, and excellent transparency and flexibility.

[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
A resin film or a polypropylene resin film, a polyester resin film, a polyamide resin film, or a resin film in which a polyvinylidene chloride resin is coated on the surface of a polyamide resin film, or
A film made of polyvinyl alcohol or ethylene-vinyl alcohol copolymer, and further, on one surface of a base film such as a plastic film, using a physical vapor deposition method (PVD method) such as a vacuum evaporation method. For example, 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 (CVD) method such as a low-temperature plasma chemical vapor deposition, for example, A vapor deposition film provided with a vapor deposition film of an inorganic oxide such as aluminum is known. These barrier materials are laminated with other plastic films or materials such as paper base materials, etc., for example, and filled and packed with various articles such as food and drink, pharmaceuticals, chemicals, daily necessities, miscellaneous goods, etc. To provide useful packaging materials.

[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. For a deposited film provided with an oxide deposited film, a deposited film can be formed on any of the base films by a vacuum deposition method or the like, but the gas barrier properties against oxygen gas, water vapor gas, and the like can be significantly improved. Whether or not it is related to the heat resistance of the substrate 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 effect such as gas barrier properties against oxygen gas is greatly reduced. It can be improved. 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 it is technically possible to form it, it is extremely difficult to greatly improve the effects such as gas barrier properties against oxygen gas, and it can be said that it is not always satisfactory. Not something. Furthermore, as the above-mentioned base film, for example, those using a polyethylene terephthalate film, the polyethylene terephthalate film has rigidity, is hard, and easily generates film wrinkles and the like. There is a problem that it is not suitable for packaging materials that require 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 a vapor-deposited film of an inorganic oxide, it is said that, during the formation of the vapor-deposited film, the thermal damage to the base film is small, and the vapor-deposited film of the inorganic oxide can be formed on various plastic films. It has advantages and has attracted much attention in recent years. For example, there has been proposed a method of forming a silicon oxide vapor-deposited film on a polyolefin resin molded article having poor heat resistance by using a plasma chemical vapor deposition method (see Japanese Patent Application Laid-Open No. 5-287103). However, in the above method, after laminating the sealant film, the oxygen gas barrier property is 20 cc / m ² or more, and it can be said that the oxygen gas barrier property that can always be sufficiently satisfied can be achieved. The fact is that there is no such thing. Further, in the above, in order to improve the oxygen gas barrier property, the thickness of the inorganic oxide vapor-deposited film must be formed to 1000 ° or more, and in such a case, the polyolefin having poor heat resistance. There is a problem that it is necessary to solve the problem of strength deterioration due to the plasma reaction of the base resin film. 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. Therefore, the present invention uses a biaxially oriented polypropylene film as a base film, has excellent gas barrier properties against oxygen gas and water vapor, etc., and further provides an inexpensive laminated material excellent in transparency, flexibility and the like. is there.

[0007]

As a result of various studies to solve the above-mentioned problems, the present inventor first focused on using a biaxially oriented polypropylene film as a base film. On one surface, a first barrier thin film mainly composed of an inorganic oxide formed by a low-temperature plasma chemical vapor deposition method is provided, and on the other hand, at least a thermoplastic resin layer, a second barrier resin layer, and a thermoplastic resin layer Attention is paid to the multilayer laminated film consisting of at least the thermoplastic resin layer, the second barrier resin layer, and the thermal barrier resin on the surface of the first barrier thin film by the co-extrusion lamination method. A laminated material is manufactured by laminating a multilayer laminated film composed of a plastic resin layer, and then, using the laminated material, a bag is produced or a box is produced to produce a packaging container, and the packaging container is formed in the packaging container. , For example, food and drink Pharmaceuticals, chemicals, daily necessities, household goods, was manufactured packaging products a variety of goods filling and packaging to the other, etc., excellent in gas barrier properties against oxygen gas,
Prevents alteration of contents, modification, etc., has a long-term stable distribution, storage suitability, etc., and also has excellent transparency, so that contents can be visually recognized from the outside. The present invention has been accomplished by finding a useful laminated material which can produce an excellent and excellent packaged product at low cost without sacrificing bag, etc. in flexibility, laminating strength and the like.

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 biaxially stretched polypropylene film by a low-temperature plasma chemical vapor deposition method. On the surface of the thin film, at least a thermoplastic resin layer by a co-extrusion lamination method,
The present invention relates to a laminated material obtained by laminating a multilayer laminated film including a second barrier resin layer and a thermoplastic resin layer.

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. FIGS. 1, 2 and 3 are schematic diagrams illustrating a few examples of the layer structure of the laminated material according to the present invention. FIG. First, as shown in FIG. 1, a laminated material 1 according to the present invention comprises a first barrier thin film 3 mainly composed of an inorganic oxide formed by a low-temperature plasma chemical vapor deposition method on one surface of a biaxially stretched polypropylene film 2.
Further, on the surface of the first barrier thin film 3, at least the thermoplastic resin layer 4, the second barrier resin layer 5, and the thermoplastic resin layer 6 are formed by a co-extrusion lamination method. The basic structure is that the multi-layer laminated film 7 is laminated. 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. An anchor coat agent is applied to the surface of the barrier thin film 3 by an anchor coat agent.
A multilayer laminated film 7 comprising at least a thermoplastic resin layer 4, a second barrier resin layer 5, and a thermoplastic resin layer 6 laminated by a co-extrusion lamination method via a coating agent layer 8. Can be mentioned. Next, as for the laminated material according to the present invention, a laminated material having still another form will be exemplified.
As b, as shown in FIG. 3, in the laminated material 1 shown in FIG. 1, on the first barrier thin film 3, directly or via a primer agent layer of a printing primer agent, One having a configuration in which the printed picture layer 9 is provided can be given. In addition, in FIG. 2 and FIG.
Symbols such as 4, 5, 6, and 7 have the same meaning as described above. The above examples illustrate a few examples of the laminate 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 the biaxially oriented polypropylene film constituting the laminated material according to the present invention, for example, Propylene homopolymers of propylene homopolymers, random or block copolymerized propylene-α-olefin copolymers of propylene-based α-olefins, and polypropylene-based resin films or sheets. Can be used. In the above, α-
Examples of the olefin include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene,
Olefinic monomers such as octene, 5-ethylidene-2-norbonene, 5-methyl-2-norbonene, and 1.4-hexadiene can be used. Further, in the present invention, as the α-olefin, for example, those graft-modified with a carboxylic acid such as maleic anhydride can be used. Thus, in the present invention, as the biaxially stretched polypropylene film, a method of forming the above-mentioned polypropylene resin alone into a film,
A method of forming a multilayer co-extrusion film using different kinds of resins, and a method of mixing two or more kinds of resins before forming a film to form a film of a polypropylene resin. Producing a film or sheet, and further, for example,
A polypropylene-based resin film or sheet stretched biaxially using a tenter method or a tuber method can be used. The thickness of the biaxially stretched polypropylene film is 5 to 20.
About 0 μm, more preferably about 10 to 50 μm is desirable. In the above, at the time of film formation of the polypropylene-based resin, for example, the workability of the film, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slip properties, mold release properties, flame retardancy, Improve anti-mold properties, electrical properties, etc.,
For the purpose of reforming, various plastic compounding agents and additives can be added, and the amount of addition can be arbitrarily added from a very small amount to several tens% depending on 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 the like can be used, and further, a modifying resin such as a polyamide-based resin and a polyolefin-based resin can be used.

In the present invention, the biaxially stretched polypropylene film may be used, if necessary, for example, by corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, chemical Pretreatment such as oxidation treatment using other treatments and the like can be arbitrarily performed. The above-mentioned surface pretreatment may be carried out in a separate step before forming the first barrier thin film mainly composed of an inorganic oxide.
In the case of a surface treatment such as a discharge treatment, a pretreatment by an in-line treatment can be performed as a pretreatment for forming the first barrier thin film mainly composed of the above-described inorganic oxide. There is an advantage that cost can be reduced. The above-mentioned surface pretreatment is performed as a method for improving the adhesion between the biaxially oriented polypropylene film and the first barrier thin film mainly composed of an inorganic oxide. Other methods include, for example, previously forming a primer-coating agent layer and an under-coating layer on the surface of a biaxially stretched polypropylene film.
A coating agent layer or a vapor-deposited anchor coating agent layer may 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 is used.
Coating can be performed by using a coating method such as a coating method, a gravure roll coating method, a kiss coating method, or the like.
The timing can be carried out as a post-process after the biaxial stretching of the biaxially stretched polypropylene film, or in-line processing of the biaxial stretching.

Next, in the present invention, a first barrier thin film mainly composed of an inorganic oxide formed by a low-temperature plasma-enhanced chemical vapor deposition, which constitutes the laminated material according to the present invention, will be described. As the first barrier thin film mainly composed of an oxide, for example, a low-temperature plasma generator or the like is used on one surface of a biaxially stretched polypropylene film using a monomer gas for vapor deposition of an organic silicon compound or the like as a raw material. Low temperature plasma chemical vapor deposition (CVD)
) To form a vapor-deposited thin film of an inorganic oxide such as silicon oxide. In the above,
As the low-temperature plasma generator, for example, it is possible to use a generator such as a high-frequency plasma, a pulse wave plasma, a microwave plasma, and so on, in the present invention,
In order to obtain highly active and stable plasma, it is desirable to use a generator using a high-frequency plasma method. Specifically, an example of a method of forming a first barrier thin film mainly composed of an inorganic oxide by the low-temperature plasma chemical vapor deposition method will be described. FIG. It is a schematic block diagram of the low-temperature plasma chemical vapor deposition apparatus which shows the outline | summary about the formation method of the 1st barrier property thin film which mainly consists of an inorganic oxide. As shown in FIG. 4, in the present invention, the biaxially stretched polypropylene film 2 is unwound from an unwinding roll 13 arranged in a vacuum chamber 12 of a low-temperature plasma chemical vapor deposition apparatus 11, and Axial stretched polypropylene film 2
It 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. While adjusting the mixed gas composition for vapor deposition, the mixed gas composition for vapor deposition was introduced into the vacuum chamber 12 through the raw material supply nozzle 19, and was transported onto the peripheral surface of the cooling / electrode drum 15 described above. Plasma is generated by the glow discharge plasma 20 on the biaxially stretched polypropylene film 2 and irradiated with the plasma to form a vapor-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 biaxially stretched polypropylene film 2 on which the deposited thin film of an inorganic oxide such as silicon oxide is formed is wound on a winding roll 24 via an auxiliary roll 23, and is subjected to low-temperature plasma chemical vapor deposition according to the present invention. A first barrier thin film mainly composed of an inorganic oxide can be produced by a method. 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 above-mentioned organosilicon compounds, 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 characteristics and the like.

In the present invention, in the case of the silicon oxide vapor-deposited thin film formed as described above, the silicon oxide vapor-deposited thin film has 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 above-mentioned first barrier thin film has silicon (Si) and oxygen (O) as essential constituent elements, and further has carbon (C) and hydrogen (H).
Is formed of a silicon oxide vapor deposited film containing one or both elements as trace constituent elements, and the thickness thereof is in the range of 50 ° to 500 °, and the above essential constituent elements and trace amounts of The composition ratio of the constituent elements changes continuously in the film thickness direction. Further, when the silicon oxide deposited thin film as the first barrier thin film contains a compound composed of carbon, the carbon content is reduced in the depth direction of the film thickness. It is assumed that. Thus, in the present invention, for the above-mentioned deposited thin film of silicon oxide as the first barrier thin film, for example, an X-ray photoelectron spectrometer (Xray Pho)
tooth Spectroscopy, X
PS), secondary ion mass spectrometer (Secondary)
Ion Mass Spectroscopy, SI
Confirming the above physical properties by performing elemental analysis of the deposited silicon oxide thin film using a method of performing ion etching in the depth direction using a surface analyzer such as MS) Can be done. In the present invention, the thickness of the silicon oxide vapor-deposited thin film as the first barrier thin film is desirably 500 mm or less, and specifically, the thickness is 50 to 50 °. 50
0 °, more preferably 100-300 ° is desirable.
If it is thicker, cracks and the like are likely to occur in the film, which is not preferable.
If it is less than this, it is difficult to achieve the effect of the barrier property, which is not preferable. In the above description, the film thickness can be measured, for example, by a fundamental parameter method using a fluorescent X-ray analyzer (model name: RIX2000 type) manufactured by Rigaku Corporation. Further, in the above, as means for changing the thickness of the deposited thin film of silicon oxide as the first barrier thin film, increasing the deposition rate of the deposited film, that is, reducing the amount of the monomer gas and oxygen gas It can be performed by a method of increasing the number or a method of reducing the deposition rate. In the case where a thin film of an inorganic oxide is formed on a substrate having low heat resistance by a low-temperature plasma chemical vapor deposition method, such as the above-described biaxially stretched polypropylene film, the film is exposed to plasma when the deposition rate is reduced. It is not preferable because the time is long, and the biaxially stretched polypropylene film and the like are deteriorated.
It is preferable to form a deposited film at a deposition rate of 200 to 200 n / min.

The first film formed as described above is
The deposited thin film of silicon oxide as a barrier thin film of
The oxygen permeability coefficient at 3 ° C. and 90% relative humidity is 3.0 × 1
^{0 -1 6 cm 3 (STP)} · cm / cm 2 · sec · cm
Hg or less. The oxygen transmission coefficient of the above-described deposited thin film of silicon oxide as the first barrier thin film can be calculated by the following method. First, the film thickness of the biaxially oriented polypropylene film is L ₁ , the oxygen permeability coefficient of the biaxially oriented polypropylene film is P ₁ , and the film thickness of the first barrier thin film mainly composed of an inorganic oxide obtained by low-temperature plasma chemical vapor deposition. Is L ₂ , the first of which is mainly composed of an inorganic oxide obtained by the low-temperature plasma chemical vapor deposition method.
The oxygen permeability coefficient of the barrier thin film is P ₂ , and the film thickness of the biaxially stretched polypropylene film and the first barrier thin film mainly composed of an inorganic oxide formed by low-temperature plasma chemical vapor deposition is P,
Assuming that the oxygen transmission coefficient between the biaxially stretched polypropylene film and the first barrier thin film mainly composed of an inorganic oxide formed by low-temperature plasma-enhanced chemical vapor deposition is P, the inorganic oxidation by low-temperature plasma-enhanced chemical vapor deposition is represented by the following equation. Permeability coefficient [cm ³ (STP) of the first barrier thin film mainly composed of a substance
Cm / cm ² · sec · cmHg] can be calculated. L / P = L ₁ / P ₁ + L ₂ / P ₂ ─────1 Equation 1 above can be converted to 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 the oxygen permeability between the biaxially oriented polypropylene film and the first barrier thin film mainly composed of an inorganic oxide formed by low-temperature plasma-enhanced chemical vapor deposition, the oxygen permeability of the biaxially oriented polypropylene film, and the low temperature. Since the oxygen permeability of the first barrier thin film mainly composed of an inorganic oxide formed by plasma enhanced chemical vapor deposition is shown, the biaxially stretched polypropylene film and the first barrier composed mainly of inorganic oxide formed by low temperature plasma chemical vapor deposition are shown. The oxygen permeability coefficient of the conductive thin film, and the oxygen permeability coefficient of the biaxially stretched polypropylene film were measured, and further, the oxygen permeability of the first barrier thin film mainly composed of an inorganic oxide by low-temperature plasma chemical vapor deposition, By multiplying the thickness of the first barrier thin film mainly composed of inorganic oxide by low-temperature plasma chemical vapor deposition, The mainly inorganic oxide according to 1
Of the barrier thin film can be calculated. In the above, the oxygen permeability is measured using, for example, an oxygen permeability measuring instrument [model name, OX-TRAN (OX-TRAN) 2/20] manufactured by MOCON, USA.
The film thickness can be measured under the conditions of 23 ° C. and 90% RH, and the film thickness can be measured by, for example, a fundamental parameter method using an X-ray fluorescence analyzer (model name: RIX2000) manufactured by Rigaku Corporation. Can be measured.

Next, in the present invention, the multilayer laminated film constituting the laminated material according to the present invention will be described. First, as the thermoplastic resin forming the thermoplastic resin layer constituting the multilayer laminated film, extrusion molding is used. And any material that can be fused and mutually fused by heat, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, polypropylene, Ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-
Methacrylic acid copolymer, ethylene-propylene copolymer, methylpentene polymer, polyolefin resin such as polyethylene or polypropylene acrylic acid,
Acid-modified polyolefin resins modified with unsaturated carboxylic acids such as methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, etc., polyvinyl acetate resins, polyester resins, polystyrene resins, etc. Resins consisting of one or more of the above resins can be used. In the present invention, when the two layers of the thermoplastic resin layer are formed using the above-described resins, they can be formed by combining the same type of resin or different types of resins. For example, it may be formed by using the same kind of polyethylene resin, or using a different kind of polyethylene resin and an ethylene-vinyl acetate copolymer, or a polyethylene resin and an ethylene-methacrylic acid copolymer. It can also be formed.

In the present invention, among the above resins, it is particularly preferable to use linear (linear) low-density polyethylene. The above-mentioned linear low-density polyethylene has the advantage of having a small amount of propagation of rupture due to its tackiness and improving impact resistance. It is also effective for preventing deterioration of environmental stress cracking properties. In the present invention,
Other resins can be blended with the linear low-density polyethylene. For example, by blending an ethylene-butene copolymer or the like, the heat stability is slightly lowered and the seal stability is deteriorated in a high temperature environment. Although there is a tendency, there is an advantage that the tearing property is improved and contributes to easy opening. Further, in the present invention, the linear low-density polyethylene as the resin having heat sealability as described above includes, specifically, ethylene-polymerized using a metallocene catalyst.
α-Olefin copolymer can be used. Examples of the ethylene-α-olefin copolymer polymerized using the metallocene catalyst include, for example, a catalyst obtained by combining a metallocene complex and alumoxane such as a catalyst obtained by combining zirconocene dichloride and methylalumoxane;
That is, an ethylene-α-olefin copolymer obtained by polymerization using a metallocene catalyst can be used. The metallocene catalyst has a non-uniform active site and is called a multi-site catalyst, whereas the existing catalyst is called a single-site catalyst because the active site is uniform. Specifically, the brand name “Kernel” manufactured by Mitsubishi Chemical Corporation, the brand name “Evolu” manufactured by Mitsui Petrochemical Industry Co., Ltd., Exxon Chemical (USA)
N Chemical Co., Ltd. product name "Exact (E
XACT) ", Dow Chemical, USA
MICAL) Affinity- (AFFI)
NITY), an ethylene-α-olefin copolymer polymerized using a metallocene catalyst such as trade name “ENGAGE”. In the present invention, ethylene-polymerized using the above metallocene catalyst
When an α-olefin copolymer is used, there is an advantage that a low-temperature heat-sealing property is possible when a bag is manufactured.

Next, in the present invention, the barrier material constituting the second barrier thin film layer has a barrier property against oxygen gas, water vapor gas, etc. It is possible to use a resin that is less adsorbed by fragrance components and the like, has a high fragrance retention property, has a property that does not cause a taste, an off-flavor, etc., and is extrudable. For example, polyacrylic resin, polymethacrylic resin, polyacrylonitrile resin, polymethacrylonitrile resin, polystyrene resin, polycarbonate resin, polyethylene terephthalate resin or its ethylene component and And / or a resin in which a part of the terephthalate component is copolymerized or modified with another di- or more polyhydric alcohol component or dicarboxylic acid component. Polyethylene naphthalate is - Doo-based resins such as polyester resins, MXD nylon (Mitsubishi Gas Chemical Co., Ltd., trade name) polyamide such as a resin,
Resins such as an ethylene-vinyl alcohol copolymer, a polyvinyl alcohol-based resin, and others can be used. Thus, in the present invention, among the above resins,
It is desirable to use a resin having a fragrance retention property and a barrier property against oxygen gas or water vapor, and specifically, for example, an ethylene-vinyl alcohol copolymer, a polyamide resin, a polyacrylonitrile resin,
Alternatively, it is desirable to use a resin rich in scent retention, barrier properties, and the like made of a polyester-based resin or the like.
In the above, particularly, as the ethylene-vinyl alcohol copolymer, the ethylene content is 20 to 65 mol%.
And the degree of saponification is preferably 90% or more. In addition,
In the present invention, when the above-mentioned ethylene-vinyl alcohol copolymer is used to form the second barrier resin layer, the second barrier resin layer is formed of the above-mentioned ethylene-vinyl alcohol copolymer. A single-layer film consisting of coalescing,
Either a film composed of a mixture of two or more ethylene-vinyl alcohol copolymers having different ethylene contents or a film composed of a mixture of two or more ethylene-vinyl alcohol copolymers having different saponification degrees. Film can also be used. In the present invention, the above ethylene-vinyl alcohol copolymer may be added to other resins, for example, α-olefins such as propylene, isobutene, 4-methyl-pentene and hexene, carboxylic acids such as itaconic acid and methacrylic acid. Alternatively, a salt, an ester, an anhydride, or a polymer such as a silane compound such as vinyltrimethoxysilane may be contained. In this case, the polymer does not affect the gas barrier properties of the ethylene-vinyl alcohol copolymer. Is desirable.

Next, in the present invention, as a method of laminating the multilayer laminated film on the first barrier thin film surface, for example, a co-extrusion lamination method can be used. Specifically, a multilayer laminated film is formed by directly extruding a molten resin extruded by at least two extruders from a single die onto a first barrier thin film surface and coating the molten resin. Can be laminated. As the thickness of each layer constituting the multilayer laminated film according to the present invention as described above, for example, the thickness of the thermoplastic resin layer is about 1 to 200 μm, preferably about 5 to 100 μm, and The second barrier resin layer has a thickness of about 1 to 100 μm, preferably about 5 to 50 μm, and furthermore, an adhesive resin layer between each layer of the thermoplastic resin layer and the second barrier resin layer. About 1 to 100 μm, preferably 5 to 50 μm
Position is desirable. The above method has advantages such as thinning of each layer, stable interlaminar adhesion, improvement of extrudability of high neck-in resin, compactness of processing machine line, and low equipment cost compared to tandem type. is there.

In the present invention, when the above-mentioned lamination is performed, if necessary, for example,
An adhesion improver such as an anchor coat agent may be coated. Specific examples of the above-mentioned anchor coating agent include organic titanium-based anchor coating agents such as alkyl titanate, isocyanate-based anchor coating agents, and polyethyleneimine-based anchoring agents. Various types of aqueous or oil-based anchor coating agents such as coating agents, polybutadiene-based anchor coating agents, and others can be used. Thus, in the present invention, the above-mentioned anchor coating agent is, for example, roll coat, gravure coat, knife coat,
An anchor coating agent layer can be formed by coating with a dip coating, a spray coating or another coating method, and drying a solvent, a diluent and the like. In the above, the coating amount of the anchor coating agent is 0.1 to 5 g.
/ M ² (dry state).

Next, in the present invention, as a print pattern layer constituting the laminated material 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 configured by forming a desired print pattern made of other materials. In the above, various ink compositions include, for example, vehicles constituting the ink composition include, for example, polyethylene resins, polyolefin resins such as chlorinated polypropylene resins, poly (meth) acrylic resins, and polyvinyl chloride. Resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate copolymer, polystyrene resin, styrene-butadiene copolymer, vinylidene fluoride resin, polyvinyl alcohol resin, polyvinyl acetal 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, xylene resin, Cellulose resins such as ionic acid resin, nitrocellulose, ethylcellulose, acetylbutylcellulose, ethyloxyethylcellulose, rubber resins such as chlorinated rubber and cyclized rubber, petroleum resins, rosin, casein A mixture of one or more natural resins such as linseed oil, oils and fats such as linseed oil and soybean oil, and other resins 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 laminated material 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 10 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.

The laminated material of the present invention produced as described above may be used as it is or, if necessary, for packaging other resin films, paper substrates, synthetic paper, cellophane, etc. The present invention is intended to manufacture various composite films by arbitrarily combining with a packaging material or the like constituting a container to produce various composite films, and to manufacture a packaging container suitable for filling and packaging various articles. That is, in the present invention, the laminated material according to the present invention or the above-described composite film is used to make a bag or a box to produce packaging containers of various forms, and thus, the above-described production is carried out. Packaging container has transparency, gas barrier properties against oxygen, water vapor, etc.,
Excellent impact resistance etc., and furthermore, laminating, printing,
It has post-processing suitability such as bag making or box making, for example, food and drink, pharmaceuticals, detergents, shampoos, oils, toothpastes, adhesives, adhesives, etc. It has excellent filling and packaging suitability, storage suitability and the like. In the above description, the method of bag making or box making will be described. For example, in the case of a soft packaging bag, the above-described laminated material or composite film is used, and the surface of the heat-sealing resin layer of the inner layer is used. Can be folded, or they can be folded or two of them can be overlapped, and the peripheral end can be heat-sealed to provide a seal portion to form a bag. Thus, as the bag making method, the above-mentioned laminated material, or the composite film, is folded with its inner layer facing the surface, or the two sheets are overlapped, and further, the peripheral edge of the outer periphery is For example, a side seal type, a two-side seal type, a three-way seal type, a four-side seal type, an envelope-attached seal type, a gasket-attached seal type (pyro-seal type),
Heat seals such as pleated seal type, flat bottom seal type, square bottom seal type, etc., to form packaging containers of various forms according to the present invention. Can be manufactured. 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, heather
As a method of sealing, for example, a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal
And a known method such as an ultrasonic seal.
In the present invention, the packaging container as described above includes, for example, a one-piece type, a two-piece type,
Other spouts or zippers for opening and closing can be arbitrarily attached.

[0024]

The present invention will be described more specifically with reference to the following examples. Example 1 (1). As a base material, a biaxially stretched polypropylene film having a thickness of 20 μm (manufactured by Nimura Chemical Industry Co., Ltd., trade name: F
OK, one-sided corona-treated product), which was mounted on a delivery roll of a low-temperature plasma-enhanced chemical vapor deposition apparatus, and the above-mentioned biaxially stretched polypropylene film was coated with a deposited silicon oxide film having a thickness of 120 mm under the following conditions. Was formed on one side. (Evaporation conditions) Mixing ratio of reaction gas: hexamethyldisiloxane: oxygen: helium = 1: 10: 10 (unit: slm) Degree of vacuum in vacuum chamber: 5.5 × 10 ⁻⁶ mbar Vacuum in evaporation chamber Degree: 6.5 × 10 ^-2 mbar Cooling / electrode drum supply power: 18 kW Film transport speed: 80 m / min Evaporation surface: Corona treated surface (2). Next, the surface of the deposited silicon oxide thin film of the biaxially stretched polypropylene film on which the deposited silicon oxide thin film was formed 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 changed from 35 dyn to 62 d
yn. Output: 10 kw Processing speed: 100 m / min (3). Next, using a biaxially stretched polypropylene film on which a vapor-deposited thin film of silicon oxide subjected to the above-described corona treatment was used, and on the vapor-deposited thin film surface of the silicon oxide, after forming a printing layer in which a white ink was entirely printed by a gravure printing machine, The biaxially stretched polypropylene film formed with the printed layer and the deposited silicon oxide thin film is mounted on a first delivery roll of a co-extrusion laminating machine, and a urethane-based anchor is formed by a gravure roll coating method. 0.5 g / m 2 of the coating agent is applied to the surface of the printing layer.
² (dry weight) was applied. (4). On the other hand, low-density polyethylene, acid-modified polyolefin resin, and ethylene-vinyl alcohol copolymer (ethylene content: 44 mol%) are individually melt-kneaded using three extruders, and the resultant mixture is mixed into one die. And then laminated inside the die, and then directly on the surface of the anchor coating agent layer of the biaxially oriented polypropylene film on which the above-mentioned anchor coating agent layer, printing layer and silicon oxide deposited thin film are formed. Co-extrusion coating, and then cooling with a metal roll to form a three-layer, five-layered multilayer film having a thickness of 70 μm, laminated on the above-mentioned anchor coating agent layer surface, The laminated material according to the present invention having the above layer configuration was produced. Biaxially oriented polypropylene film with a thickness of 20 μm, deposited thin film of silicon oxide / printing layer / anchor coating agent layer / low density polyethylene layer with a thickness of 15 μm / acid-modified polyolefin layer with a thickness of 5 μm / ethylene with a thickness of 10 μm -Vinyl alcohol copolymer layer / acid-modified polyolefin layer having a thickness of 5 μm / thickness of 35 μm
m low-density polyethylene layer The surface of the low-density polyethylene layer was treated with ozone.

Embodiment 2 (1). As a base material, a biaxially oriented polypropylene film having a thickness of 20 μm (trade name, Q, manufactured by Nimura Chemical Industry Co., Ltd.)
HI, one-sided corona-treated product), which was mounted on a delivery roll of a low-temperature plasma-enhanced chemical vapor deposition apparatus, and the above-described biaxial stretching was performed on a deposited silicon oxide thin film having a thickness of 150 ° under the following conditions. It was formed on one side of a polypropylene film. (Evaporation conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen: helium = 1: 11: 10 (unit: slm) Degree of vacuum in vacuum chamber: 5.2 × 10 ⁻⁶ mbar Vacuum in evaporation chamber Degree: 5.1 × 10 ^-2 mbar Cooling / electrode drum supply power: 18 kW Film transport speed: 70 m / min Evaporation surface: Corona treated surface (2). Next, the surface of the deposited silicon oxide thin film of the biaxially stretched polypropylene film on which the deposited silicon oxide thin film was formed was subjected to corona treatment under the following conditions. As a result, the surface tension of the surface of the deposited thin film of silicon oxide was changed from 42 dyn to 65 d.
yn. Output: 10 kw Processing speed: 100 m / min (3). Next, using a biaxially stretched polypropylene film on which a vapor-deposited thin film of silicon oxide subjected to the above-described corona treatment was used, and on the vapor-deposited thin film surface of the silicon oxide, after forming a printing layer in which a white ink was entirely printed by a gravure printing machine, The biaxially stretched polypropylene film formed with the printed layer and the silicon oxide vapor-deposited thin film is mounted on a first delivery roll of a co-extrusion laminating machine, and an imine-based one-liquid is formed by a gravure roll coating method. An anchor coat agent of the type was applied to the above-mentioned print layer surface at a rate of 0.4 g / m ² (dry weight). (4). On the other hand, polypropylene (ethylene-propylene random copolymer), acid-modified polyolefin resin, ethylene-vinyl alcohol copolymer (ethylene content of 44
Mol%) were separately melt-kneaded using three extruders, supplied to one die, and laminated inside the die.
Then, the biaxially stretched polypropylene film, on which the above-mentioned anchor coating agent layer, printing layer, and silicon oxide vapor-deposited thin film are formed, is directly co-extruded and coated on the surface of the anchor coating agent layer. Cooled with a metal roll to obtain a 70 μm thick
A seed laminated four-layer film was formed and laminated on the above-mentioned anchor coating agent layer surface to produce a laminated material according to the present invention having the following layer constitution. Biaxially-stretched polypropylene film with a thickness of 20 μm, deposited thin film of silicon oxide / printing layer / anchor coating agent layer / acid-modified polyolefin layer with a thickness of 15 μm / ethylene-vinyl alcohol copolymer layer with a thickness of 10 μm / 15 μm-thick acid-modified polyolefin layer / 30 μm-thick polypropylene layer The acid-modified polyolefin layer was not subjected to ozone treatment.

Example 3 Example 3 was carried out in the same manner as in Example 1 except that the vapor deposition conditions and the layer structure of the multilayer laminated film were changed as follows. (Evaporation conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen: helium = 1: 14: 12 (unit: slm) Degree of vacuum in vacuum chamber: 5.5 × 10 ⁻⁶ mbar Vacuum in evaporation chamber Degree: 6.5 × 10 ^-2 mbar Cooling / electrode drum supply power: 15 kW Film transport speed: 90 m / min Evaporation surface: Corona treated surface Evaporation film thickness: 110Å (multilayer laminated film) Low-density polyethylene, acid-modified Polyolefin resin and MXD nylon (manufactured by Mitsubishi Gas Chemical Industry Co., Ltd.) are individually melt-kneaded using three extruders, supplied to one die, laminated inside the die, and Co-extrusion coating directly on the surface of the anchor coating agent layer of a biaxially stretched polypropylene film formed with an anchor coating agent layer, a printing layer, and a deposited silicon oxide thin film.
Then, after cooling with a metal roll, a three-layer, four-layer laminated film having a thickness of 70 μm was formed.
The laminated material according to the present invention having the following layer constitution was manufactured by laminating on the coating agent layer surface. Biaxially oriented polypropylene film with a thickness of 20 μm, evaporated thin film of silicon oxide / printed layer /
Anchor coating agent layer / Low density polyethylene layer having a thickness of 15 μm / acid-modified polyolefin layer having a thickness of 5 μm / thickness of 10
μm MXD nylon layer / 5 μm-thick acid-modified polyolefin layer / 35 μm-thick low-density polyethylene layer The low-density polyethylene layer was ozone-treated.

Example 4 Example 4 was carried out in the same manner as in Example 2 except that the vapor deposition conditions and the layer constitution of the multilayer laminated film were changed as follows. (Evaporation conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen: helium = 1: 15: 13 (unit: slm) Degree of vacuum in vacuum chamber: 5.5 × 10 ⁻⁶ mbar Vacuum in evaporation chamber Degree: 6.5 × 10 ^-2 mbar Cooling / electrode drum supply power: 17 kW Film transport speed: 65 m / min Evaporation surface: Corona treated surface Evaporation film thickness: 165Å (multilayer laminated film) Low-density polyethylene, acid-modified Polyolefin resin and MXD nylon (manufactured by Mitsubishi Gas Chemical Industry Co., Ltd.) are individually melt-kneaded using three extruders, supplied to one die, laminated inside the die, and Co-extrusion coating directly on the surface of the anchor coating agent layer of a biaxially stretched polypropylene film formed with an anchor coating agent layer, a printing layer, and a deposited silicon oxide thin film.
After that, it was cooled by a metal roll to form a three-layer, five-layered multilayer film having a thickness of 70 μm, and the above anchor was formed.
The laminated material according to the present invention having the following layer constitution was manufactured by laminating on the coating agent layer surface. Biaxially oriented polypropylene film with a thickness of 20 μm, evaporated thin film of silicon oxide / printed layer /
Anchor coating agent layer / acid-modified polyolefin layer having a thickness of 15 μm / MXD nylon layer having a thickness of 10 μm / thickness of 15
μm acid-modified polyolefin layer / 30 μm-thick polypropylene layer The acid-modified polyolefin layer was not subjected to ozone treatment.

Comparative Example 1 (1). As a base material, a biaxially stretched polypropylene film having a thickness of 20 μm (manufactured by Nimura Chemical Industry Co., Ltd., trade name: F
OK, one-sided corona-treated product), which was mounted on a delivery roll of a low-temperature plasma-enhanced chemical vapor deposition apparatus, and the above-mentioned biaxially stretched polypropylene film was coated with a deposited silicon oxide film having a thickness of 120 mm under the following conditions. Was formed on one side. (Evaporation conditions) Mixing ratio of reaction gas: hexamethyldisiloxane: oxygen: helium = 1: 10: 10 (unit: slm) Degree of vacuum in vacuum chamber: 5.5 × 10 ⁻⁶ mbar Vacuum in evaporation chamber Degree: 6.5 × 10 ^-2 mbar Cooling / electrode drum supply power: 18 kW Film transport speed: 80 m / min Evaporation surface: Corona treated surface (2). Next, the surface of the deposited silicon oxide thin film of the biaxially stretched polypropylene film on which the deposited silicon oxide thin film was formed 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 changed from 35 dyn to 62 d
yn. Output: 10 kw Processing speed: 100 m / min (3). Next, using a biaxially stretched polypropylene film on which a vapor-deposited thin film of silicon oxide subjected to the above-described corona treatment was used, and on the vapor-deposited thin film surface of the silicon oxide, after forming a printing layer in which a white ink was entirely printed by a gravure printing machine, A co-extrusion of the printed layer and a biaxially oriented polypropylene film on which a silicon oxide deposited thin film has been formed;
Then, a urethane-based anchor coating agent was applied to the print layer surface at a rate of 0.5 g / m ² (dry weight) by a gravure roll coating method. (4). On the other hand, a low-density polyethylene is used, and the biaxially-stretched polypropylene film formed with the above-mentioned anchor coating agent layer, printing layer, and silicon oxide vapor-deposited thin film through an extruder die. 70 μm thick on the surface of the agent layer
And then cooled by a metal roll, and a 70 μm-thick low-density polyethylene layer is laminated on the surface of the above-mentioned anchor coating agent layer. Lumber was manufactured. Biaxially oriented polypropylene film with a thickness of 20 μm, evaporated silicon oxide thin film / printed layer / anchor
Coating agent layer / low-density polyethylene layer having a thickness of 70 μm The surface of the low-density polyethylene layer was treated with ozone.

Comparative Example 2 A laminated material having the following layer structure was prepared in the same manner as in Comparative Example 1 except that the reaction gas mixture ratio during the deposition conditions was changed as follows. Manufactured. (Evaporation conditions) Mixing ratio of reaction gas: hexamethyldisiloxane: oxygen: helium = 1: 2.5: 2 (unit: slm) Biaxially stretched polypropylene film having a thickness of 20 µm, evaporated silicon oxide thin film / printed layer / anchor -Coating agent layer / thickness 7
0 μm low density polyethylene layer The low density polyethylene layer surface was ozone treated.

Comparative Example 3 (1). As a base material, a biaxially stretched polypropylene film having a thickness of 20 μm (manufactured by Nimura Chemical Industry Co., Ltd., trade name: F
OK, one-sided corona-treated product), which was mounted on a delivery roll of a take-up type vacuum vapor deposition apparatus (physical vapor phase epitaxy), and a silicon oxide vapor-deposited thin film having a thickness of 500 mm was formed under the following conditions. On one side of a biaxially oriented polypropylene film. (Evaporation conditions) Target: granular silicon monoxide (SiO) Reactive gas: oxygen gas Heating method: electron beam method (80 mA) Degree of vacuum in evaporation chamber: 3.0 × 10 ⁻⁶ mbar Cooling drum temperature : -10 ° C Film transport speed: 490 m / min Deposition surface: Corona treated surface (2). Next, using a biaxially stretched polypropylene film on which a silicon oxide vapor-deposited thin film was formed as described above, a printing layer formed by printing a white ink on the entire surface of the silicon oxide vapor-deposited thin film using a gravure printing machine was formed. On the surface, a two-component curable polyurethane-based laminate using a gravure roll coating method.
The coating adhesive was applied at a rate of 0.5 g / m ² (dry weight). Then, a low-density polyethylene film having a thickness of 70 μm was dry-laminated on the surface of the adhesive layer to produce a laminated material having the following layer constitution. Biaxially oriented polypropylene film with a thickness of 20 μm, evaporated silicon oxide thin film / printed layer / adhesive layer / low density polyethylene film with a thickness of 70 μm

EXPERIMENTAL EXAMPLE 1 The biaxially stretched polypropylene film formed on each of the above Examples 1-4 and Comparative Examples 1-3 formed with a vapor-deposited thin film of silicon oxide, and a laminated material were prepared using the following data. Was measured. (1). Measurement of Oxygen Permeability This was measured at a temperature of 23 ° C. and a humidity of 0% RH and 90% RH with a measuring instrument (model name, OXTRAN) manufactured by MOCON, USA. (2). Color evaluation Color evaluation was performed by visual observation of coloring. The visual observation of coloring was made by directly observing 10 samples by visual observation. The above measurement results are shown in Tables 1 and 2 below.

[0032]

[Table 1] Biaxially stretched polypropylene film formed with a deposited thin film of silicon oxide,

[0033]

[Table 2] Measurement results of oxygen permeability for laminated materials

Experimental Example 2 The oxygen transmission coefficient of a biaxially stretched polypropylene film on which a silicon oxide vapor-deposited thin film was formed was calculated based on the above formulas 1 and 2. The results are shown in Table 3 below.

[0035]

Table 3 Results of oxygen permeability coefficient (23 ° C / 90% RH)

As is clear from the results shown in Table 2 above.
In addition, the laminated materials according to Examples 1 to 4 have an oxygen permeability of 0
% RH and 90% RH.
c / m ^Two· Day · atm or less. In contrast, the ratio
The laminates according to Comparative Examples 1 to 3 have an oxygen permeability of about 3
0cc / m^Two・ Day ・ atm or more. this is,
The laminated material according to Examples 1 to 4 is the same as the first barrier thin film.
By providing the second barrier resin layer, the oxygen permeability is improved.
It shows that the excess can be improved. Also,
From the results shown in Table 3, those according to Examples 1 to 4 indicate that
Elemental transmission coefficient is 3.0 × 10^-16The following
And those of Comparative Examples 1-2 were 4.0 × 10^-16Over
Comparative Example 3 was 6.0 × 10^-15more than
The film composition of Comparative Examples 1 to 3 has a large oxygen permeability.
It shows that it becomes.

[0037]

As is apparent from the above description, the present invention focuses on the use of a biaxially stretched polypropylene film as a base film, and on one surface thereof, an inorganic oxide film formed by low-temperature plasma chemical vapor deposition. A first barrier thin film mainly composed of a material is provided, and on the other hand, focusing on at least a multilayer laminated film including a thermoplastic resin layer, a second barrier resin layer, and a thermoplastic resin layer, And a multilayer laminated film comprising at least the thermoplastic resin layer, the second barrier resin layer, and the thermoplastic resin layer, which are laminated by the co-extrusion lamination method. Producing materials, then using the laminated material, producing 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 packaging products, which have excellent gas barrier properties against oxygen gas, and prevent long-term alteration and reforming of the contents, and stably distribute them for a long period of time. , Storage suitability, etc., and excellent transparency, so that the contents can be visually recognized from the outside, and furthermore, the flexibility, the laminating strength, etc. do not have a bag breakage and are extremely excellent. A useful laminate that can produce good packaging products at low cost can be produced. That is, since the laminated material according to the present invention is mainly composed of a polyolefin-based resin film called a biaxially oriented polypropylene film, the laminated material has flexibility and has an oxygen gas barrier property of 10 cc / m even under high humidity conditions. ^2.
day · atm or less, and furthermore, the barrier property can be improved even if the thickness of the deposited film is small, and as a result, the manufacturing cost can be reduced. Even if a vapor-deposited film is formed on a biaxially stretched polypropylene film having low heat resistance by a low-temperature plasma chemical vapor deposition method, there is an advantage that thermal damage due to this can be avoided.

[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 is a schematic cross-sectional view schematically illustrating a layer configuration of still another example of the laminated material according to the present invention.

FIG. 4 shows an outline of a method for forming a first barrier thin film mainly composed of an inorganic oxide by low-temperature plasma chemical vapor deposition on one surface of a biaxially stretched polypropylene film according to the present invention. It is a schematic structure figure of a vapor deposition device.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Laminated material 1a Laminated material 1b Laminated material 2 Biaxially stretched polypropylene film 3 First barrier thin film 4 Thermoplastic resin layer 5 Second barrier resin layer 6 Thermoplastic resin layer 7 Multilayer laminated film 8 Anchor coat Agent layer 9 Print pattern layer 11 Low temperature plasma chemical vapor deposition device 12 Vacuum chamber 13 Unwinding roll 14 Auxiliary roll 15 Cooling / electrode drum 16 Gas supply device 17 Gas supply device 18 Raw material volatile supply device 19 Raw material supply nozzle 20 Glow discharge plasma 21 Power supply 22 Magnet 23 Auxiliary roll 24 Winding roll 25 Vacuum pump

Continuation of the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (reference) // C08J 7/00 303 C08J 7/00 303 4K030 7/06 7/06 Z F term (reference) 3E086 AD01 AD02 AD03 BA04 BA14 BA15 BA40 BB01 BB22 BB90 CA01 CA11 CA28 4F006 AA12 AA19 AB13 AB15 AB16 AB20 AB23 AB24 AB35 AB38 AB65 AB67 AB68 BA01 BA05 BA13 DA01 DA03 DA04 EA05 4F073 AA17 BA08 BB01 CA02 CA70 FA08 4F100 AA01A03 AK03 AK01 AK01 AK01 AK01 AK01 AK01 AK01 AK01 AK69D AL07 BA05 BA07 BA10A BA26 CB02 EC14C EH23C EH66B EJ38A EJ65C GB15 GB23 HB31C JB16C JB16E JD02B JD02D JD03 JD03C JD04 JK17 JL02 JN01 YY00 YY00C 4K01 BA03 BA08 AA11 AA00 BC

Claims (7)

[Claims] 1. A first barrier thin film mainly composed of an inorganic oxide formed by a low-temperature plasma chemical vapor deposition method on one surface of a biaxially stretched polypropylene film, and a first barrier thin film is further provided on a surface of the first barrier thin film. A laminated material obtained by laminating a multilayer laminated film comprising at least a thermoplastic resin layer, a second barrier resin layer, and a thermoplastic resin layer by a co-extrusion lamination method. 2. A method according to claim 1, wherein the first barrier thin film is provided on at least a thermoplastic resin layer and a second layer by a co-extrusion lamination method through an anchor coat agent layer made of an anchor coat agent. The laminated material according to claim 1, wherein a multilayer resin film composed of a barrier resin layer and a thermoplastic resin layer is laminated. 3. A method according to claim 1, wherein the first barrier thin film is directly or through a primer agent layer of a printing primer agent.
The laminated material according to claim 1 or 2, wherein a printed picture layer is provided. 4. The first barrier thin film has silicon (Si) and oxygen (O) as essential constituent elements, and further has one or both of carbon (C) and hydrogen (H). Element as a trace constituent element, and the thickness thereof is in the range of 50 to 500 °, and the constituent ratio of the essential constituent element and the trace constituent element is The laminated material according to claim 1, 2 or 3, wherein the laminated material continuously changes in a direction. 5. A silicon oxide vapor-deposited film having an oxygen transmission coefficient of 3.0 × 10 ⁻¹⁶ cm at a temperature of 23 ° C. and a relative humidity of 90%.
5. The laminate according to claim 4, wherein the thickness is not more than ³ (STP) · cm / cm ² · sec · cmHg. 6. The multilayer laminated film comprises at least a polyolefin-based resin layer, an ethylene-vinyl alcohol copolymer layer having an ethylene content of 20 to 65 mol%, and a polyolefin-based resin layer. Is 10 to 200 μm, and the ethylene-
6. The laminate according to claim 1, wherein the thickness of the vinyl alcohol copolymer layer is 2 to 50 [mu] m. 7. The laminate has an oxygen permeability of 10 cc / m ² · day · at a temperature of 23 ° C. and a relative humidity of 90% RH.
atm or less.
The laminate according to 2, 3, 4, 5 or 6.