JP2000263727A - Laminated material and packaging container using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated material having excellent transparency and high barrier properties against oxygen gas, steam or the like, rich in aroma retentivity, impact resistance, thrust resistance, the preservability of content or the like, having post-processing aptitude, excellent in laminate strength and good in filling and packaging aptitude to content, especially, a liquid seasoning and a packaging container using the same. SOLUTION: One layer of an inorg. oxide membrane 2 or a multilayered layer of two or more membranes 2 is provided on one surface of a barrier nylon film 1 and a barrier resin layer 3 comprising a resin compsn. containing a barrier polyester resin as a main component of a vehicle is provided on the inorg. oxide membrane 2 and at least a heat-sealable resin layer 4 is further laminated on the barrier resin layer 3.

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 a packaging container using the same, and more particularly, to transparency,
Excellent in barrier properties against oxygen gas, water vapor, etc., fragrance retention, impact resistance, piercing resistance, laminating strength, preservability against contents, etc., food packaging field, pharmaceutical packaging field, detergent,
Shampoos, oils, and various articles in the non-food field such as toothpaste, in particular, filling and packaging suitability for liquid seasonings such as dressing, oil, soy sauce, miso, sauce, vinegar, mayonnaise, Further, the present invention relates to a laminated material having microwave oven suitability and excellent post-process suitability, and a packaging container using the same.

[0002]

2. Description of the Related Art Conventionally, various packaging materials having a barrier property against oxygen gas, water vapor and the like and having good storage suitability have been developed and proposed.
As one of them, on a flexible plastic substrate,
There has been proposed a transparent barrier film having a structure provided with a deposited film of an inorganic oxide such as silicon oxide and aluminum oxide, a packaging laminate and a packaging container using the same.
This is excellent in transparency, and has a high barrier property against water vapor, oxygen gas, etc., as compared with a conventional aluminum foil, a laminate material for packaging using a polyvinylidene chloride resin-coated nylon film or the like. Has fragrance retention properties, etc.,
There is no environmental problem at the time of disposal, and the demand for packaging materials and the like is greatly expected.

[0003]

However, the barrier performance of the above-mentioned transparent barrier film, a laminated material for packaging using the transparent barrier film, and the like, is lower than that of a barrier material such as aluminum foil for oxygen gas and water vapor. There is a problem that it is inferior. For this reason, in the above-mentioned transparent barrier film, a packaging laminate using the same, in order to improve the barrier performance, it is necessary to increase the thickness of the deposited film, or, together with the barrier layer, of the entire layer of the laminate. Attempts have been made to increase the thickness. However, in the transparent barrier film as described above, and a packaging laminate using the same, the barrier layer itself composed of a deposited film of an inorganic oxide is inferior in flexibility. Or, if it is bent, cracks are easily generated in the deposited film. For example, when the above operation is employed during post-processing such as printing and laminating, cracks are easily generated, and cracks are generated once. Then, there is a problem that the barrier properties are significantly reduced. Further, in the above-mentioned transparent barrier film, and in a packaging laminate and the like using the same, for example, in order to improve the barrier properties, when trying to increase the thickness of the vapor deposition film, conversely, the vapor deposition film By increasing the film thickness, cracks and the like are more likely to occur, and have the same problems as described above. Further, in the above-mentioned transparent barrier film, and in a packaging laminate using the same, when this causes a dimensional change or the like due to moisture absorption, the deposited film is difficult to follow the dimensional change, and cracks are easily generated. Also have the same problems as described above. In addition, when the above film thickness is improved, the deposited film is colored. For example, when used as a packaging material, there is a problem that the commercial value of the contents is significantly impaired. Next, when a film or sheet of another resin is extruded on the transparent barrier film as described above and subjected to a coating process or a dry laminating process or the like, a transparent laminate film is produced. There is also a problem that the adhesive strength between the barrier film and the laminating adhesive, the anchor coating agent, etc. is low. Therefore, such a decrease in the laminating strength often results in the formation of a bag. However, there is a problem that delamination or the like is caused in the laminated material. In particular, when a liquid or viscous content such as a liquid seasoning is filled and packaged as a content, the laminated material constituting the bag is affected by the content and lacks laminate strength. There is a problem that a peeling phenomenon or the like is caused between the layers and the use is not performed. Thus, in order to improve the above-mentioned laminate strength and the like, pretreatment such as corona treatment may be performed, but the effect is not so much recognized in the transparent barrier film, and conversely,
There is a problem that the deposited layer is damaged. Further, when filling and packaging the above-mentioned liquid seasoning, etc., those using a nylon film or the like as a base film on which an inorganic oxide vapor-deposited film is provided are compared with those using a polyethylene terephthalate film, There is a problem that the fragrance retention and the like are inferior due to the difference in fragrance retention of the base film itself. Further, in the above case, on the inorganic oxide deposited film, further,
Although a transparent barrier film in which a gas barrier coating is coated with a coating agent containing a metal alkoxide compound or a hydrolyzate as a main component has been proposed, it is compared with a substrate film using a polyethylene terephthalate film as a base film. In fact, it is not possible to solve the problem of poor scent retention and the like. Therefore, the present invention has excellent transparency and high barrier properties against oxygen gas, water vapor, etc.
Rich in fragrance retention, impact resistance, piercing resistance, storage stability to contents, etc., and has post-processing suitability.
It is an object of the present invention to provide a laminated material having excellent strength and good suitability for filling and packaging of contents, particularly liquid seasonings, and a packaging container using the same.

[0004]

As a result of various studies to solve the above-mentioned problems, the present inventor has a barrier property against oxygen gas, water vapor and the like, and is excellent in impact resistance, puncture resistance and the like. , Combined with a tough biaxially stretched barrier nylon film, a thin film of inorganic oxide, a barrier resin layer of a barrier polyester resin, etc.,
Focusing on an organic and inorganic silane coupling agent, an extensible polyurethane-based resin, a polyester-based resin, and the like, first, a thin film of inorganic oxide is formed on one surface of the barrier nylon film. A layer or a multilayer film comprising two or more layers, and, if necessary, a primer composition containing a silane coupling agent or a primer composition containing a polyester-based resin on the inorganic oxide thin film. A barrier resin layer made of a resin composition containing a barrier polyester-based resin as a main component of the vehicle is provided through the thin film, and further, on the barrier resin layer,
If necessary, at least a heat-sealing resin layer is laminated via an anchor coat agent layer or an adhesive layer for laminating to produce a laminated material. Using a material to make a bag or a box to produce a packaging container, and then filling and packaging the contents in the packaging container, especially liquid or viscous contents such as a liquid seasoning, It has excellent transparency and high barrier properties against oxygen gas or water vapor, etc., and also has excellent fragrance retention, impact resistance, piercing resistance, laminating strength, etc., and liquid seasonings, etc. Has excellent storage stability for liquid or viscous contents, and
There is no crack at the time of post-processing, it has extremely high post-processing suitability, and even if the packaged product is microwaved,
The present invention has been completed by finding that it is possible to manufacture a laminated material having sufficient microwave oven suitability and a packing suitability for various articles as a packaging material and a packaging container and the like using the same. is there.

[0005] That is, the present invention relates to a method of forming one layer or two layers of an inorganic oxide thin film on one surface of a barrier nylon film.
A barrier resin layer of a resin composition containing a barrier polyester-based resin as a main component of a vehicle, and a barrier resin layer formed on the inorganic oxide thin film. On the layer, at least
TECHNICAL FIELD The present invention relates to a laminated material having a configuration in which a conductive resin layer is laminated, and a packaging container using the laminated material.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. First, the configuration of the laminated material according to the present invention and the packaging container using the same will be described with reference to the drawings by exemplifying a few of them. FIGS. FIG. 5 and FIG. 6 are schematic cross-sectional views showing the layer structure of the laminated material, and FIG. 5 and FIG. It is.

First, as shown in FIG. 1, a laminated material A according to the present invention comprises, on one surface of a barrier nylon film 1, one layer of an inorganic oxide thin film 2 or a multilayer of two or more layers. A film (not shown) is provided, and a barrier resin layer 3 made of a resin composition containing a barrier polyester resin as a main component of a vehicle is provided on the inorganic oxide thin film 2. The basic structure is such that at least a heat-sealing resin layer 4 is laminated on the barrier resin layer 3. As a specific example of the laminated material according to the present invention, as shown in FIG. 2, in the laminated material A shown in FIG.
If necessary, a coating thin film 5 of a primer composition containing a silane coupling agent or a primer composition containing a polyester-based resin was provided between the barrier resin layer 3 and the barrier resin layer 3, and both were laminated. Laminated material B composed of
Can be mentioned. Further, as another specific example of the laminated material according to the present invention, as shown in FIG.
Between the barrier resin layer 3 and the heat-sealing resin layer 4,
If necessary, at least the barrier resin layer 3 can be provided via the anchor coating agent layer 6 or the laminating adhesive layer 6a.
And a heat-sealing resin layer 4. Further, as another specific example of the laminated material according to the present invention, as shown in FIG. 4, the above-mentioned coating thin film 5 and the anchor
Laminated material D having a configuration provided in combination with the adhesive agent layer 6 or the laminating adhesive layer 6a. Thus, the above-mentioned examples are a few examples constituting the laminated material according to the present invention, and the present invention is not limited thereto.For example, in the present invention, although not illustrated, In addition to the heat-sealing resin layer, etc., other base materials may be arbitrarily laminated according to the purpose of use, the contents to be filled and packaged, the distribution channel, the sales form, the use, etc. It is possible to design and manufacture a laminated material. In the present invention, the inorganic oxide thin film, the coating thin film, and the barrier resin layer, the anchor coating agent layer, or the laminating adhesive layer have an effect such as close adhesion. In order to play, it is important that they are laminated adjacent to each other in this order, but each other base material is used for its purpose,
Depending on the application or the like, various types of laminated materials can be designed and manufactured by arbitrarily laminating.

Next, in the present invention, the structure of the packaging container according to the present invention, which is formed by using the above-mentioned laminated material to form a bag or a box, will be described. By way of example, a description will be given of a packaging container made from a bag or a box using the laminated material A shown in FIG. 1, as shown in a schematic perspective view of FIG. Prepared, and the heatsink located on the innermost layer
The surfaces of the conductive resin layers 4 and 4 are superimposed on each other, and then the three sides of the outer peripheral edge are heat-sealed to form the seal portions 7, 7, and 7. , A three-way seal type flexible packaging container E can be manufactured. Thus, in the above three-way seal type flexible packaging container E, the contents are filled through the upper opening, and then the opening is heat-sealed to prepare various packages. Products can be manufactured.

Alternatively, in the present invention, as the packaging container according to the present invention, as shown in the schematic perspective view of FIG. 6, the laminated material A shown in FIG. The surfaces of the heat-sealable resin layers 4 and 4 are superposed on each other, and then both ends of the outer periphery are heat-sealed to form seal portions 7 and 7. Thus, the two-way seal type flexible packaging container F according to the present invention can be manufactured. Thus, in the above-mentioned two-way seal type flexible packaging container F, the contents are filled from the upper opening, and thereafter, the opening is heat sealed. do it,
Various packaging products can be manufactured. In the present invention, it is needless to say that the present invention is not limited to the above-illustrated packaging container, and that various types of packaging containers can be manufactured depending on the purpose, application, and the like. Needless to say.

Next, in the present invention, the materials constituting the laminated material, the packaging container and the like according to the present invention as described above, the manufacturing method thereof, and the like will be described.
The laminate material according to the present invention, as a barrier nylon film constituting a packaging container, etc., itself has a gas barrier property against oxygen gas, water vapor and the like, and has impact resistance,
Any polyamide-based resin film or sheet that is excellent in piercing resistance and the like, has high toughness, and can hold an inorganic oxide thin film can be used. Specifically, for example, MXD nylon 6 film,
A multilayer laminated film consisting of two or more layers of MXD nylon resin and various polyamide resins such as nylon 46, nylon 6, nylon 66, nylon 610, nylon 612, nylon 11, nylon 12, and others; Vinyl alcohol copolymer and the above nylon 46, nylon 6, nylon 66, nylon 6
10, nylon 612, nylon 11, nylon 12,
A multilayer laminated film composed of two or more layers with various other polyamide-based resins can be used.
In the above multilayer laminated film, between each layer,
For example, polyethylene resin, polypropylene resin,
Lamination can be performed via an adhesive resin layer such as an acid-modified polyolefin-based resin or the like. Thus, the above MXD
Nylon 6 film, or multilayer laminated film,
It is desirable to use a biaxially stretched barrier nylon film that has been biaxially stretched by a normal biaxial stretching method such as a tenter system or a tuber system.
As the film thickness, about 10 to 200 μm, preferably,
About 10 to 50 μm is desirable. If necessary, the MXD nylon film or the multilayer laminated film may be provided with a surface smoothing treatment coated with an anchor coating agent or the like, or a corona discharge treatment, a plasma discharge treatment, a flame treatment, an ozone treatment, or the like. Arbitrary pre-processing such as processing can also be performed. In the present invention, by using the above-mentioned barrier nylon film as a base material, it has a barrier property against oxygen gas, water vapor, and the like, and further, has strength, impact resistance, puncture resistance, and the like. By using the toughness, a laminated material having these characteristics is manufactured.

In the present invention, the method for producing the above-mentioned multilayer laminated film will be described. Examples of the production method include a molding method for forming a resin into a multilayer film with different properties, such as a T-die method and an inflation method. Is adopted. Specifically, using a multilayer T die-casting method such as a feed block method or a multi-manifold method, or a molding method such as a multilayer inflation molding method, for example, a nylon resin layer / acid-modified polyolefin Multi-layer laminated film consisting of three types of five layers, such as adhesive resin layer composed of resin-based resin / ethylene-vinyl alcohol copolymer layer / adhesive resin layer composed of acid-modified polyolefin-based resin / nylon resin layer, or nylon resin Layer / ethylene-vinyl alcohol copolymer layer / nylon resin layer, or a multilayer laminated film of two or three layers such as nylon resin layer / MXD nylon resin layer / nylon resin layer. is there. Next, in the present invention, 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 nylon resin layer is about 1 to 200 μm, preferably 5 to 200 μm.
About 50 μm is desirable, and as an ethylene-vinyl alcohol copolymer layer or an MXD nylon resin layer, about 1 to 100 μm, preferably 5 to 50 μm
Is desirable, and as an adhesive resin layer between the respective layers,
About 1 to 100 μm, preferably about 5 to 50 μm is desirable. In the above, the ethylene-vinyl alcohol copolymer has, for example, a vinyl acetate content of about 79%.
An ethylene-vinyl alcohol copolymer having an ethylene content of 25 to 50 mol%, which is obtained by completely saponifying an ethylene-vinyl acetate copolymer of about 92 wt%, can be used.

Next, in the present invention, the inorganic oxide thin film constituting the laminate, the packaging container and the like according to the present invention will be described. The inorganic oxide thin film is basically a metal oxide. Any film can be used as long as it is an amorphous (amorphous) thin film. For example, silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), Sodium (Na), boron (B), titanium (Ti), lead (P
b), a thin film in which an oxide of a metal such as zirconium (Zr) or yttrium (Y) is made amorphous can be used. Thus, a thin film obtained by converting the above metal oxide into an amorphous state can be referred to as a metal oxide such as silicon oxide, aluminum oxide, magnesium oxide, or the like. _X ,
AlO _X, MO _X as such as MgO _X (However, in the formula,
M represents a metal element, and the value of X has a different range depending on the metal element. ). The range of the value of X is 0 to 2 for silicon (Si), 0 to 1.5 for aluminum (Al), and magnesium (Mg).
Is 0 to 1, calcium (Ca) is 0 to 1, potassium (K) is 0 to 0.5, tin (Sn) is 0 to 2, sodium (Na) is 0 to 0.5, Boron (B)
1, 5, 0 for titanium (Ti), 0 for lead (Pb)
-1, zirconium (Zr) can take a value of 0-2, and yttrium (Y) can take a value of 0-1.5.
In the above, when X = 0, it is a perfect metal, it is not transparent and cannot be used at all, and the upper limit of the range of X is a completely oxidized value. In the present invention,
As a packaging material, generally, there are few examples used except for silicon (Si) and aluminum (Al). Silicon (Si) is 1.0 to 2.0, aluminum (Al)
Can be used in the range of 0.5 to 1.5.

In the present invention, the inorganic oxide thin film includes one of the above-described inorganic oxide thin films,
Alternatively, an inorganic oxide thin film composed of a multilayer film of two or more inorganic oxide thin films is used. Thus, in the present invention, a method of forming one or two or more multilayer films of inorganic oxide thin films on a barrier nylon film will be described.
Physical vapor deposition methods such as a vacuum deposition method, a sputtering method, and an ion plating method.
Deposition method, PVD method) or a chemical vapor deposition method (Chemical Vap method) such as a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, or a photochemical vapor deposition method.
or Deposition method, CVD method) and the like. In the present invention, to further explain the film-forming method, for example, using a metal oxide as a raw material as described above, a vacuum evaporation method of heating and vaporizing and vapor-depositing on a barrier nylon film, Alternatively, an oxidation reaction deposition method in which a metal or metal oxide is used as a raw material, oxygen is introduced and oxidized to deposit on a barrier nylon film, and a plasma-assisted oxidation method in which an oxidation reaction is assisted by plasma. An evaporation film can be formed using a reactive evaporation method or the like. Further, in the present invention, when forming a deposited film of silicon oxide, the deposited film can be formed by a plasma enhanced chemical vapor deposition method using organosiloxane as a raw material. In the present invention, the thickness of the above-mentioned inorganic oxide thin film varies depending on the type of the metal or metal oxide to be used.
The thickness of the layer is about 50 to 2000 °, preferably
It is desirable to arbitrarily select and form the thickness in the range of about 100 to 1000 °, and the thickness of the multilayer film of two or more inorganic oxide thin films is about 100 to 4000 °, preferably 120 to 2000 °. The position is the desired one.

In the present invention, a specific example of a method for forming a multilayer film having one or two or more inorganic oxide thin films is shown in FIG. 7. FIG. 7 shows an example of a roll-up type vacuum evaporator. It is a schematic block diagram. As shown in FIG. 7, in the vacuum chamber 111, the barrier nylon film 113 unwound from the unwind roll 112 passes through the coating drum 114 and enters the vapor deposition chamber 115, where The evaporation source heated in the crucible 116 is evaporated, and further, if necessary, while oxygen or the like is jetted from the oxygen blowing port 117, on the above-mentioned barrier nylon film 113 on the cooled coating drum 114,
An inorganic oxide vapor-deposited film is formed through the masks 118, 118, and then the barrier nylon film 113 on which the vapor-deposited film is formed is fed into the vacuum chamber 111, and further wound around a take-up roll 119. By taking this, a barrier nylon film 11 having an inorganic oxide thin film
3 can be manufactured. Thus, in the present invention, the above-described film formation is repeated or, although not shown, the above-mentioned winding vacuum evaporator is connected in two or more to continuously evaporate. By doing
An inorganic oxide thin film comprising two or more multilayer films of an inorganic oxide thin film can be formed.

Further, in the present invention, a specific example of a film forming method in which two or more inorganic oxide thin films are laminated by the above-described plasma chemical vapor deposition method will be described. FIG.
1 is a schematic configuration diagram illustrating an example of a plasma chemical vapor deposition apparatus. As shown in FIG.
The barrier nylon film 214 is unwound from the unwinding roll 213 disposed in the vacuum chamber -212, and is further conveyed at a constant speed via the auxiliary roll 215. On the surface, a mixed gas composed of, for example, an organic silicon compound, an oxygen gas, an inert gas, or the like, supplied from the raw material volatile supply devices 217, 218, and 219 is introduced through the raw material supply nozzle 220, and the glow discharge plasma 221 On one surface of the barrier nylon film 214, a thin film of an inorganic oxide such as a silicon oxide vapor-deposited film is formed to form a film, and the cooling / electrode drum 216 is disposed outside the vacuum chamber-212. A predetermined voltage is applied from a power supply 222 which is in use, and a magnet 223 is disposed near the cooling / electrode drum 216. To promote the development of plasma, then,
The barrier nylon film 214 on which a thin film of an inorganic oxide such as a silicon oxide vapor-deposited film is formed,
5 and wound on a take-up roll 224 to produce a barrier nylon film having a thin film of inorganic oxide. Thus, in the present invention, the above-described film formation is repeated or, although not shown, the above-described plasma chemical vapor deposition apparatus is connected in two or more to continuously deposit. Thus, an inorganic oxide thin film composed of two or more multilayer films of an inorganic oxide thin film can be formed. In the figure, 225
Represents a vacuum pump.

Further, in the present invention, as a method of forming a multilayer film of two or more inorganic oxide thin films, the above-mentioned physical vapor deposition such as a vacuum deposition method, a sputtering method, and an ion plating method may be used. Inorganic oxide thin film consisting of a combination of a chemical vapor deposition (PVD) method and a chemical vapor deposition method (CVD method) such as a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, or a photochemical vapor deposition method. Is formed into a film by laminating two or more layers, thereby making it possible to produce an inorganic oxide thin film composed of a multilayer film of two or more inorganic oxide thin films.
That is, although not shown, first, a thin film of the first inorganic oxide is formed using the above-mentioned winding vacuum evaporator, and then the above-described plasma chemical vapor deposition is performed on the thin film of the inorganic oxide. Forming a second inorganic oxide thin film using the apparatus;
With the first and second inorganic oxide thin films, an inorganic oxide thin film composed of a multilayer film of two or more inorganic oxide thin films can be formed. In the above, the order of film formation may be any, for example, first, film formation using a roll-up vacuum evaporation machine, then may be formed using a plasma chemical vapor deposition apparatus, Film formation may be performed in the reverse order.

In the above, the thin film mainly composed of a deposited silicon oxide film as the inorganic oxide thin film is made of a silicon compound containing at least silicon and oxygen as constituent elements,
Further, it is preferable that one or more elements of carbon or hydrogen are contained as trace constituent elements, and that the film thickness is in the range of 50 to 500 °. Thus, in the present invention, as the silicon oxide thin film as described above, an organic silicon compound is used as a raw material, and a vapor deposition film formed by a plasma chemical vapor deposition method using a low-temperature plasma generator or the like is used. be able to. In the above, as the organic silicon compound, for example, 1.1.3.3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethyl Silane, 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 properties and the like. Further, in the above, as the low-temperature plasma generator, for example, a high-frequency plasma, a pulse wave plasma, a microwave plasma or the like generator may be used.
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.

Next, in the present invention, a barrier resin layer made of a resin composition containing a barrier polyester-based resin as a main component of a vehicle and constituting a laminate, a packaging container and the like according to the present invention will be described. As the conductive resin layer, first, for example, one or more barrier polyester-based resins are used as a main component of the vehicle, and
Further, if necessary, for example, fillers, stabilizers, plasticizers,
Light stabilizers such as antioxidants and ultraviolet absorbers, dispersants, thickeners, desiccants, lubricants, antistatic agents, cross-linking agents, and other additives are optionally added, and solvents and diluents are sufficient. Into a solvent type, an aqueous type having a solid content of about 5 to 30% by weight,
Alternatively, a resin composition composed of an emulsion type or the like is prepared. Thus, in the present invention, the above-mentioned resin composition is used, for example, a roll coating method, a gravure roll coating.
Coating amount by a coating method such as a coating method, a kiss roll coating method, a squeeze roll coating method, a reverse roll coating method, a curtain flow coating method, etc. , for ^{example, 0.1g / m 2 ~20g / m} 2 ( dry state) position, ^{preferably, 1g / m 2 ~10g / m} 2 ( dry state) position, more preferably, 3g / m ² ~5g / m
Coating so as to be in the ² (dry state) position, followed by heat drying and further aging treatment to form the barrier resin layer according to the present invention.
In the present invention, as the above additives,
The barrier polyester-based resin reacts with a hydroxyl group or a carboxyl group or the like at the terminal thereof,
It is preferable to add a polyfunctional isocyanate compound capable of forming a crosslinked structure (three-dimensional network structure).

In the above description, the barrier polyester resin has, for example, an excellent gas barrier property against oxygen gas or water vapor, and an excellent barrier property against odor as compared with polyolefin resins such as polyethylene and polypropylene. A polyester resin having a scent-retaining property of the contents can be used. In particular,
Examples of the barrier polyester resin include, for example, polycondensation of one or more aromatic saturated dicarboxylic acids having a benzene nucleus such as terephthalic acid as a basic skeleton and one or more saturated divalent alcohols. A thermoplastic polyester resin can be used. In the above description, as the aromatic saturated dicarboxylic acid having a benzene nucleus as a basic skeleton, for example, terephthalic acid, isophthalic acid, phthalic acid, diphenyl ether-4, 4-dicarboxylic acid, and the like can be used. In the above, as the saturated divalent alcohol, ethylene glycol, propylene glycol, trimethylene glycol-
, Tetramethylene glycol, diethylene glycol
, Polyethylene glycol, polypropylene glycol
1, aliphatic glycols such as polytetramethylene glycol, hexamethylene glycol, dodecamethylene glycol, neopentyl glycol, and alicyclic glycols such as cyclohexanedimethanol. 2-bis (4'-β
-Hydroxyethoxyphenyl) propane, naphthalenediol, other aromatic diols and the like can be used. In the present invention, the above-mentioned saturated aromatic dicarboxylic acid having a benzene nucleus as a basic skeleton further includes, for example, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, Sebacic acid, one or more of aliphatic saturated dicarboxylic acids such as dodecanoic acid can be added for copolycondensation, and the amount thereof is based on the amount of aromatic saturated dicarboxylic acid having a benzene nucleus as a basic skeleton. It is preferable to add about 1 to 10% by weight for use. Further, in the present invention, the above-mentioned saturated divalent alcohol can be co-polycondensed using another divalent or polyvalent alcohol as described above.

In the present invention, specific examples of the barrier polyester resin include thermoplastic polyethylene terephthalate resin formed by polycondensation of terephthalic acid and ethylene glycol, and terephthalic acid. Thermoplastic polybutylene terephthalate resin formed by polycondensation with tetramethylene glycol, thermoplastic polycyclohexane dimethylene terephthalate formed by polycondensation of terephthalic acid with 1,4-cyclohexanedimethanol Resin, thermoplastic polyethylene terephthalate resin formed by copolycondensation of terephthalic acid, isophthalic acid and ethylene glycol, copolymer of terephthalic acid, ethylene glycol and 1,4-cyclohexanedimethanol Thermoplastic polyethylene terephthalate resin produced by polycondensation, Tal acid and isophthalic acid and ethylene glycol - le and propylene glycol - thermoplastic polyethylene terephthalate produced by co-polycondensation of Le - DOO resins, polyester polyol - can be used Le resin, other like. In particular, in the present invention, the above-mentioned barrier polyester resin comprises a polycondensation of ethylene glycol and terephthalic acid, and further comprises a part of the ethylene glycol component and terephthalic acid component with adipic acid and isophthalic acid. It is preferable to use a modified polyester resin modified with an acid and polycondensed.

In the present invention, the barrier polyester resin as described above has a glass transition point in the range of 0 ° C. to 80 ° C., more preferably 45 ° C. to 7 ° C.
It is desirable to use one in the range of 5 ° C., and it is desirable to use one having a molecular weight in the range of 1,000 to 30,000, more preferably 10,000 to 25,000. In the above, the glass transition point is 0 ° C., and further, when the temperature is 45 ° C. or less, lacks gas barrier properties against oxygen gas, water vapor, or the like, or lacks in scent retention properties against odors, and the effect is reduced. Blocking, heat
If the glass transition point is 75 ° C. or more, more preferably 80 ° C. or more, it is not preferable because it is taken out to the hot plate at the time of sealing and the filling suitability is lowered due to the reduced slipperiness. This is not preferred because of the fact that the pinhole resistance, filling suitability and the like are lowered. Further, in the above, when the molecular weight is 1,000, and further, when it is 10,000 or less, it lacks gas barrier properties against oxygen gas, water vapor, or the like, or lacks in fragrance retention properties against odors, and is not preferable because its effect is thin. Having a molecular weight of 2500
If it is 0, or more than 30,000, the packaging material becomes hard, and as a so-called liquid sachet filled with a small amount of a packaging container, in particular, a liquid seasoning, etc., the pinhole resistance,
It is not preferable because the suitability for filling and the opening property (cutting property) are lowered.

In the present invention, the above-mentioned barrier polyester resin is used as a main component of the vehicle, and if necessary, an additive is optionally added thereto, and the mixture is sufficiently kneaded with a solvent, a diluent or the like. A barrier resin layer formed by preparing a resin composition, coating it by a normal coating method, and then performing heat drying and further aging treatment, is formed of an inorganic oxide. It is excellent in close adhesion to a thin film, the bonding strength between the two is extremely strong, and no phenomenon such as peeling between the layers is observed. Further, in the present invention, the inorganic oxide thin film and the above-mentioned barrier resin layer And the two layers synergistically constitute a barrier film, whereby the barrier property against oxygen gas, water vapor gas and the like is remarkably improved, and the barrier property against the smell of the content is improved. Excellent flavor properties, further, transparency, heat resistance, hot water resistance, laminating - DOO aptitude, superior to other such, as it is capable of producing a very good laminate.

Next, in the present invention, in the laminate or packaging container according to the present invention, a primer containing a silane coupling agent is interposed between the above-mentioned inorganic oxide thin film and the barrier resin layer. Providing a coating thin film of a composition or a primer composition containing a polyester resin,
Both can be laminated. Thus,
As the primer composition containing the silane coupling agent, specifically, a polyurethane-based resin composition containing a silane coupling agent and a filler, or a water / alcohol-based composition containing a silane coupling agent is used. The composition can be used. In the above, as the silane coupling agent constituting the polyurethane resin composition, an organic functional silane monomer having a binary reactivity can be used. For example, γ-chloropropyltrimethoxysilane, vinyltrichlorosilane , Vinyltriethoxysilane, vinyl-tris (β-methoxyethoxy) silane,
γ-methacryloxypropyltrimethoxysilane, β
-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, N-β (aminoethyl)-
γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane, γ- One or more of aqueous solutions of aminopropylsilicone and the like can be used. In the silane coupling agent as described above, a functional group at one end of the molecule, usually, a chloro, alkoxy, or acetoxy group, or the like is hydrolyzed to form a silanol group (SiOH). The metal constituting the thin film of the substance, or an active group on the surface of the thin film of the inorganic oxide, for example, a functional group such as a hydroxyl group, by some action, for example, causes a reaction such as a dehydration condensation reaction, and the thin film of the inorganic oxide A silane coupling agent is modified on the surface by a covalent bond or the like, and a strong bond is formed on the surface of the inorganic oxide thin film of the silanol group itself by adsorption or hydrogen bonding. On the other hand, an organic functional group such as vinyl, methacryloxy, amino, epoxy, or mercapto at the other end of the silane coupling agent is formed on a thin film of the silane coupling agent, for example, a barrier resin layer, Reacts with substances constituting other layers to form a strong bond. Thus, in the present invention, the thin film of the inorganic oxide and the barrier resin layer are firmly and tightly adhered to each other by the above-mentioned chemical bonding and the like, so that the laminating strength is increased and the laminating strength is improved. This makes it possible to form a highly rigid laminated structure. In the present invention, the inorganic and organic properties of the silane coupling agent are utilized to improve the tight adhesion between the inorganic oxide thin film and the barrier resin layer, thereby improving the laminating strength and the like. Is to increase.

Next, in the present invention, examples of the filler constituting the polyurethane resin composition include calcium carbonate, barium sulfate, alumina white, silica, talc, glass frit, resin powder, and the like. Can be used. This is to adjust the viscosity and the like of the polyurethane-based resin composition to enhance the coating suitability and the like.

Further, in the present invention, as the polyurethane resin constituting the above-mentioned polyurethane resin composition, for example, a polymer obtained by reacting a polyfunctional isocyanate with a hydroxyl group-containing compound, specifically, For example, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate and polymethylene polyphenylene polyisocyanate, or hexamethylene diisocyanate, xylylene diisocyanate and the like. One-pack or two-pack polyurethane obtained by the reaction of a polyfunctional isocyanate such as an aliphatic polyisocyanate described above with a hydroxyl group-containing compound such as a polyether polyol, a polyester polyol or a polyacrylate polyol. A system resin can be used. Thus, in the present invention, by using the polyurethane resin as described above, the elongation of the coating thin film is improved, for example, by laminating or
The purpose of the present invention is to improve the suitability for post-processing such as bag making, and to prevent the occurrence of cracks and the like in the inorganic oxide thin film during post-processing.

Thus, in the present invention, the polyurethane resin composition may be a polyurethane resin,
30% by weight, silane coupling agent, 0.05 to
About 10% by weight, preferably 0.1% to 5% by weight
%, About 0.1-20% by weight of filler, preferably 0.5
If necessary, additives such as a stabilizer, a curing agent, a cross-linking agent, a lubricant, an ultraviolet absorber, etc. are optionally added, and a solvent, a diluent, etc. are added. And thoroughly mixed to prepare a polyurethane resin composition. Thus, in the present invention, the above-mentioned polyurethane-based resin composition is, for example, roll-coated, gravure-coated,
Coating is performed on the inorganic oxide thin film by knife coating, dip coating, spray coating, or other coating methods, and then the coating film is dried to remove the solvent, diluent, and the like. Thus, the coating thin film according to the present invention can be formed. In the present invention, the thickness of the coating thin film made of the polyurethane resin composition is, for example, about 0.01 to 50 μm, preferably about 0.1 to 50 μm.
About 1 to 5 μm is desirable. In the present invention, the polyurethane-based resin composition may further include, if necessary, for example, a cellulose derivative such as nitrocellulose,
Other binders can be optionally added.

Next, in the present invention, a water / alcohol-based composition containing the above-mentioned silane coupling agent will be described. In the present invention, one or more of the above-mentioned silane coupling agents may contain a solvent. Water (100)% as a diluent, or at least ethanol containing water
Water / alcohol composition containing a silane coupling agent by adding a solvent or diluent consisting of a simple substance or a mixture such as ethyl alcohol, isopropyl alcohol (IPA) or ethyl acetate, and sufficiently dissolving or mixing. Adjust things. next,
In the present invention, the water / alcohol-based composition prepared as described above may be used, for example, in roll coating, gravure coating, knife coating, dip coating, spray coating, and other coating methods. Then, the coating film is dried on the inorganic oxide thin film, and then the coating film is dried to remove the solvent, the diluent and the like, whereby the coated thin film according to the present invention can be formed. In the present invention, it is most preferable that the thickness of the coating thin film is, for example, that the coating thin film is formed in a state of a monomolecular film by a silane coupling agent. It is desirable that the film thickness be in the order of ten to several thousand degrees, and more preferably, several μm. In the above, when preparing a water / alcohol-based composition containing a silane coupling agent, if necessary, additives such as a binder such as a resin, a stabilizer, a filler, a lubricant, an ultraviolet absorber, and others are used. It can be arbitrarily added. Also,
In the water / alcohol composition containing the silane coupling agent, the content of the silane coupling agent is about 0.05 to 10% by weight, preferably 0.1 to 5%.
% By weight, and the content of water is as follows.
0-100% by weight, preferably 5.0-75% by weight
And the content of alcohol is preferably
It is desirably about 0.5 to 75% by weight, preferably about 1.0 to 50% by weight. Thus, in the present invention, as described above, by chemical bonding with a silane coupling agent or the like,
The inorganic oxide thin film and the barrier resin layer are firmly and tightly adhered to each other to increase the laminating strength and to form a strong laminated structure having a high laminating strength. Furthermore, in the present invention, the inorganic and organic properties of the silane coupling agent are utilized to improve the tight adhesion between the inorganic oxide thin film and the barrier resin layer, thereby improving the laminating properties. It increases the strength and the like.

Next, the laminated material according to the present invention described above,
The coating thin film made of a primer composition containing a polyester resin constituting a packaging container or the like will be described. A thermoplastic polyester resin produced by the polycondensation of one or more aromatic saturated dicarboxylic acids with one or more saturated divalent alcohols can also be used.

Thus, in the present invention, the primer composition containing the above-mentioned polyester-based resin contains one or more of the above-mentioned polyester-based resins as a main component of a vehicle. One or more additives such as silane coupling agents, fillers, stabilizers, curing agents, cross-linking agents, lubricants, ultraviolet absorbers, etc. are optionally added, and a solvent, diluent, etc. are sufficiently added. To prepare a primer composition containing a polyester resin.
Thus, in the present invention, a primer composition containing the polyester resin as described above is used, for example, by roll-coating.
Coating on an inorganic oxide thin film by a coating method, gravure coating, knife coating, dip coating, spray coating, or another coating method, and then drying the coating film to form a solvent. By removing the diluent and the like, the coating thin film according to the present invention can be formed. In the present invention, the thickness of the coating thin film of the polyester resin composition is, for example, 0.01 to 50 μm.
And preferably about 0.1 to 5 μm. In the present invention, by providing a coating thin film of the primer composition containing the above-mentioned polyester-based resin, the tight adhesion between the inorganic oxide thin film and the barrier resin layer is improved, and the odor of the contents is improved. This has the advantage of improving the fragrance retention and the like against the like.

Next, in the present invention, the heat-sealing resin forming the heat-sealing resin layer constituting the laminated material, the packaging container and the like according to the present invention is formed by melting by heat and mutual heat. A resin film or sheet that can be fused to a resin can be used. Specifically, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, polypropylene , Ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene Activate copolymer, methylpentene polymer, polybutene polymer, polyolefin resin such as polyethylene or polypropylene. Le acid, methacrylic acid, maleic acid,
Acid-modified polyolefin resin modified with unsaturated carboxylic acids such as maleic anhydride, fumaric acid, itaconic acid, etc., polyvinyl acetate resin, poly (meth) acrylic resin, polyvinyl chloride resin, and other resins. Film or sheet
Can be used. Thus, the above-mentioned film or sheet can be used in a state of a coating film of a composition containing the resin. The thickness of the film, film or sheet is 5 μm to 30 μm.
0 μm is preferable, and more preferably 10 μm to 150 μm.
μm is desirable.

In the present invention, the above-mentioned heat seal
It is particularly preferable to use an ethylene / α-olefin copolymer polymerized using a metallocene catalyst as the heat-sealing resin forming the hydrophilic resin layer. Thus, as the ethylene / α-olefin copolymer polymerized using the above metallocene catalyst, for example, a catalyst obtained by combining a metallocene complex such as a catalyst obtained by combining zirconocene dichloride and methylalumoxane with alumoxane, And an ethylene-α-olefin copolymer obtained by polymerization using a metallocene catalyst. Metallocene catalyst, the current catalyst,
The active sites are heterogeneous and are called multi-site catalysts, whereas the active sites are uniform and are also called single-site catalysts. Specifically, the product name "Kernel" manufactured by Mitsubishi Chemical Corporation, the product name "Evolu" manufactured by Mitsui Petrochemical Industry Co., Ltd., the product name "EXACT" manufactured by EXXON CHEMICAL, USA (EXACT) ", a product name" AFFINITY ", a product name" Engage (E) "manufactured by DOW CHEMICAL, USA.
NGAGE) or the like, and an ethylene / α-olefin copolymer polymerized by using a metallocene catalyst. Thus, in the present invention, the ethylene / α-olefin copolymer polymerized by using the metallocene catalyst as described above is a film or sheet of a heat-sealing resin constituting the innermost layer, or It functions as a film, and its low-temperature heat sealability makes it possible to prevent the occurrence of cracks or the like occurring in a thin film of an inorganic oxide during post-processing such as bag making. is there. The thickness of the film, film or sheet is about 3 μm to 300 μm, preferably 5 μm to 100 μm.
Position is desirable. In the present invention, the ethylene-α-olefin copolymer obtained by polymerization using the above-mentioned metallocene catalyst is further added to, for example, partially cross-linked ethylene-propylene rubber (EPDM) and ethylene-propylene rubber (EPR). Styrene-butadiene-styrene block copolymer (SBS), styrene-isobutylene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer (SEB)
A heat-sealing resin layer made of a resin composition to which one or more kinds of thermoplastic elastomers such as S) are added can also be used. In the present invention, as the heat-sealing resin layer, for example, an ethylene-α-olefin copolymer obtained by polymerization using the above-mentioned metallocene catalyst and a low-density polyethylene (linear low-density polyethylene) ) And a co-extruded film formed by co-extruding them.

Next, in the present invention, the above-mentioned heat seal
As a method of laminating a conductive resin layer, for example,
Laminated via a laminating adhesive layer
Dry lamination method or melt extrusion welding
Pressing through lamination through resin layer
It can be performed by a lamination method or the like. Above
Here, as the adhesive for laminating, for example, one liquid,
Alternatively, two-pack cured or uncured vinyl
System, (meth) acrylic system, polyamide system, polyester
System, polyether system, polyurethane system, epoxy system,
Solvent-based, water-based, emulsion, etc.
Adhesives for laminating, such as lamination type, can be used.
You. Thus, coating of the above-mentioned adhesive for laminating.
As a method, for example, direct gravure roll coating
Method, gravure roll method, kiss coat method, reverse
Roll coat method, Fonten method, transfer roll
It can be applied by a coating method or other methods.
The coating amount is 0.1 to 10 g / m^Two(Dry
State), more preferably 1 to 6 g / m^Two(Dry
State) is desirable. In the present invention, the above-mentioned la
Examples of the adhesive for minerals include a silane coupling agent.
And the like can be optionally added. Next
In the above, as the melt-extruded adhesive resin,
The above-mentioned thermoplastic resin forming the thermoplastic resin layer is similarly
Can be used. Thus, in the present invention,
Extruded adhesive resin is especially suitable for low density polyethylene.
Especially low-density linear polyethylene, acid-modified polyethylene
Ethylene, polymerized using a metallocene catalyst
It is preferable to use an α-olefin copolymer or the like.
It is. Melt extrusion by the above-mentioned melt extrusion adhesive resin
The thickness of the extruded resin layer is about 5 to 100 μm,
Preferably, it is about 10 to 60 μm. In addition,
In the light, the extrusion lamination method described above is used.
When, for example, to improve the tight adhesion, etc.
For example, organic titanium-based anchors such as alkyl titanate
Coating agent, isocyanate-based anchor coating agent, polyether
Thylene imine-based anchor coating agent, polybutadiene-based
Various types of aqueous or oily agents such as anchor coating agents and others
Can be used. Thus,
Examples of the coating method for the above-mentioned anchor coating agent include the following.
For example, direct gravure roll coating, gravure roll
-Lukot method, kiss coat method, reverse roll coating
Method, Fonten method, transfer roll coating method,
Can be applied by other methods,
The amount is 0.1 to 10 g / m ^Two(Dry state)
More preferably, 0.5 to 6 g / m^Two(Dry state)
Good.

In the present invention, the adhesive for laminating is, in particular, an adhesive for laminating by forming a film by a curing reaction between polyester polyol or polyether polyol and isocyanate. It is preferable to form using an agent. Specifically, polymers obtained by reacting the above-mentioned polyfunctional isocyanate with a hydroxyl group-containing compound, for example, tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate And polyfunctional isocyanates such as aliphatic polyisocyanates such as hexamethylene diisocyanate and xylylene diisocyanate, and polyether polyols and polyester polyols. A laminating adhesive composition containing a one-pack or two-pack curable polyurethane resin obtained by reaction with a hydroxyl group-containing compound such as polyacrylate polyol as a main component of a vehicle. For example, roll coat, gravure coat, knife coat, dip coat, spray - DOO, other co - plating method in co - can form a preparative adhesive layer - and coating, the solvent, and drying the diluent or the like, laminating constituting the laminate according to the present invention. In the above, the thickness of the laminating adhesive layer is as follows:
It is desirably about 0.1 to 6 g / m ² (dry state). Thus, in the present invention, by using the polyurethane resin as described above, the elongation of the thin film constituting the adhesive layer is improved in the same manner as described above, for example, by laminating or manufacturing. It is intended to improve the suitability for post-processing such as bag processing and prevent the occurrence of cracks and the like in the inorganic oxide thin film during post-processing.

In the present invention, the laminating adhesive layer formed by a curing reaction between the polyester polyol or polyether polyol and the isocyanate constituting the laminate according to the present invention. As for No. 4 dumbbell according to JIS K6301, 23
300 mm / min. In an environment of 50 ° C. and 50% RH. It is desirable that the material has a tensile elongation of 300% to 550% when measured under the following speed conditions. In the present invention, the tensile elongation of the adhesive layer for laminating is determined by a thin film of an inorganic oxide constituting a laminate, a barrier resin layer, an adhesive layer for laminating, and a heat-sealing resin. It is intended to improve the tight adhesion with a layer or the like, thereby preventing the occurrence of cracks or the like in the inorganic oxide thin film. In the above, if the tensile elongation is less than 300%, it lacks flexibility, and cracks and the like occur in the thin film of the inorganic oxide in laminating or post-processing such as bag making or box making, which is not preferable. On the other hand, when the tensile elongation exceeds 550%, the flexibility becomes excessive and the tearing property is poor.
It is not preferable because the openability of the packaging container is poor.

In the laminate according to the present invention,
Any of the layers that make up this, for example, text, graphics,
A printed pattern layer composed of a pattern, a symbol and the like can be formed. As the print pattern layer, for example, an ink composition such as a usual gravure ink composition, offset ink composition, letterpress ink composition, screen ink composition, etc. is formed on the first barrier thin film. Using a printing method such as a gravure printing method, an offset printing method, a letterpress printing method, a silk screen printing method, or the like. Can be constituted by forming a printed pattern of

Next, in the present invention, low density polyethylene having barrier properties against water vapor, water, etc.
Medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, a film or sheet of a resin such as an ethylene-propylene copolymer, or a polyvinyl alcohol having a barrier property against oxygen, water vapor, and the like, A film or sheet of a resin such as a saponified ethylene-vinyl acetate copolymer, a coloring agent such as a pigment added to the resin, and other various light-shielding properties obtained by adding and kneading a desired additive to form a film. A colored resin film or sheet can be used. These materials can be used alone or in combination of two or more. The thickness of the film or sheet is as follows:
Although it is optional, it is usually preferably about 5 μm to 300 μm, more preferably about 10 μm to 100 μm.

In the present invention, since the packaging container is usually subjected to severe physical and chemical conditions, strict packaging suitability is required for the packaging material constituting the packaging container. And various conditions such as deformation prevention strength, drop impact strength, pinhole resistance, heat resistance, sealability, quality maintenance, workability, hygiene, etc. are required. Any material that satisfies the above conditions can be selected and used.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-ethyl acrylate copolymer, ethylene-acrylic acid or methacrylic acid copolymer, Chillpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, poly (meth) acrylic resin, polyacrylonitrile resin, Polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin, polycarbonate resin, polyvinyl alcohol Resin, saponified ethylene-vinyl acetate copolymer, fluororesin,
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 can be used in 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. In the present invention, any one of the layers constituting the laminated material according to the present invention may be formed by, for example, offset printing, gravure printing, silk screen printing, or any other desired method including characters, figures, patterns, symbols, etc. It goes without saying that a print pattern layer can also be formed.

Next, in the present invention, a method of making a bag or a box using the above-mentioned laminated material will be described. For example, when the packaging container is a soft packaging bag made of a plastic film or the like, Using a laminated material manufactured by such a method, the heat-sealing resin layer of the inner layer is made to face the surface thereof, and the heat-sealing resin layer is folded, or the two sheets are overlapped, and the peripheral end is further folded. A bag can be formed by providing a seal portion by heat sealing. Thus, as the bag making method, the above-mentioned laminated material is folded with its inner layer facing the surface, or two of them are overlapped,
Further, the peripheral end portion of the outer periphery is formed, for example, by a side seal type, a two-side seal type, a three-side seal type, a four-side seal type, an envelope-attached seal type, and a gasket-attached seal type ( According to the present invention, a heat seal is formed according to a heat seal form such as a (pyrro-seale type), a pleated seal type, a flat bottom seal type, a square bottom seal type, and the like. Various forms of packaging containers can be manufactured. Others, for example, self-supporting packaging bags (standing pouches)
Can be manufactured, and in the present invention, a tube container or the like can also be manufactured using the above-mentioned laminated material. In the above, as a method of heat sealing, for example, a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high-frequency seal, an ultrasonic seal
Can be performed by a known method such as In the present invention, a spout such as a one-piece type, a two-piece type, or the like, or a zipper for opening and closing can be arbitrarily attached to the packaging container as described above.

In the present invention, the packaging container manufactured as described above can be used for various foods and drinks, chemicals such as adhesives and pressure-sensitive adhesives, cosmetics, pharmaceuticals, and other various articles, particularly,
It is used for filling and packaging of liquid or viscous articles such as liquid seasonings. Thus, in the present invention, when the packaging container according to the present invention is filled with contents, particularly liquid or viscous contents such as a liquid seasoning, the contents affect the inner surface of the bag. Since a phenomenon such as delamination often occurs and is not necessary, the thin film of the inorganic oxide and the heat-sealing resin constituting the laminated material may be used in the laminated material constituting the bag. It is desirable that the peel strength in water between the layer and the layer be 50 g / 15 mm width or more, and that the peel strength at 25 ° C. be 200 g / 15 mm width or more. In the above, if the peel strength in water is less than 50 g / 15 mm width, for example, in the case of applications such as sterilization in hot water such as boiling and retort, or in the case of using under high humidity, the packaging material When the peel strength at 25 ° C. is less than 200 g / 15 mm width, it is not preferable because sufficient strength cannot be obtained and, for example, the oxygen gas barrier property is lowered. This is not preferable because practical strength cannot be obtained. The laminated material according to the present invention can be used as a lid material, for example, by being attached to a flange portion of a plastic molded container.

[0040]

EXAMPLES The present invention will be described more specifically with reference to examples. Example 1 First, on the other surface of an MXD biaxially stretched nylon 6 film having a thickness of 15 μm, using a chemical vapor deposition method (CVD),
A silicon oxide deposited film having a thickness of 200 ° was formed. On the other hand, as a silane coupling agent, N-β (aminoethyl)-
Using γ-aminopropyltrimethoxysilane, 1.0% by weight of the silane coupling agent, 1.0% by weight of silica powder, 13 to 15% by weight of polyurethane resin, 3 to 4% by weight of nitrocellulose, and toluene 31 Polyurethane-based resin compositions were prepared which consisted of about 38% by weight, 29% to 30% by weight of methyl ethyl ketone (MEK), and 15% to 16% of isopropyl alcohol (IPA). Next, using the above-mentioned polyurethane-based resin composition, this is coated on the surface of the deposited silicon oxide film having a thickness of 200 ° formed above using a gravure roll coating method. , 10
The coating was dried at 0 ° C. for 5 seconds to form a coating thin film (thickness: 0.4 g / m ² , dry state) made of the polyurethane resin composition. Next, 10 parts by weight of a barrier polyester resin is added to 90 parts by weight of a mixed solvent of toluene and methyl ethyl ketone (1: 1) on the surface of the coating thin film formed above, and the resin composition is sufficiently kneaded. The product was coated by a gravure roll coating method to form a coating film having a thickness of 3.0 g / m ² (dry state), and then heated and dried at 120 ° C. for 30 seconds. This was processed to form a barrier resin layer. Next, on the surface of the barrier resin layer formed as described above, a two-component curable polyurethane-based resin composed of polyester polyol and isocyanate and an anchor cone composed of a 7% ethyl acetate and toluene solution were used.
Using a gravure roll coating method, this was coated to a film thickness of 1 μm to form an anchor coating agent layer, and then applied to the surface of the anchor coating agent layer. Using a linear low-density polyethylene and an ethylene-α-olefin copolymer obtained by polymerization using a metallocene catalyst,
Each was co-extruded to a thickness of 30 μm to form a heat-sealing resin layer composed of a co-extruded film having a thickness of 60 μm, and a laminated material according to the present invention having the following layer constitution was produced. MXD biaxially stretched nylon 6 film / silicon oxide deposited film / coated thin film / barrier resin layer / anchor
Coating agent layer / heat-sealing resin layer Using the laminated material produced above, a three-sided seal-type plastic bag is produced by a die-roll filling and packaging machine, and a liquid seasoning is filled. Thereafter, when the opening was heat-sealed to produce a filled packaging product, the product had a high barrier property, no deterioration of the barrier property was observed, and the barrier property against the odor of the contents was found. It also has excellent fragrance retention properties, and furthermore, very good results with excellent laminating strength.

Example 2 First, using a multilayer T-die casting method, a nylon resin layer / adhesive resin layer composed of an acid-modified polyolefin resin / ethylene-vinyl alcohol copolymer layer / acid-modified polyolefin resin was used. A multilayer laminated biaxially stretched film composed of three types of adhesive resin layer / nylon resin layer is produced, and then one of the nylon resin layer surfaces of the multilayer laminated biaxially stretched film is subjected to physical vapor deposition (PVD). ), A deposited film of aluminum oxide having a thickness of 200 ° was formed. On the other hand, thermoplastic polyethylene terephthalate resin,
5 parts by weight of toluene and methyl ethyl ketone (1: 1)
A mixed solvent of the following, a primer composition containing a polyester resin sufficiently kneaded at 95 parts by weight to prepare a primer composition,
Next, using the primer composition containing the polyester-based resin, the surface of the above-formed 200-mm-thick aluminum oxide film is coated by a gravure roll coating method. The coating was dried at 120 ° C. for 20 seconds to form a coated thin film (thickness: 0.3 g / m ² , dry state) using a primer composition containing a polyester resin. Next, 8 parts by weight of the barrier polyester resin was added to 92 parts by weight of a mixed solvent composed of toluene and ethyl acetate (1: 1) on the surface of the coated thin film formed above, and kneaded well. The resin composition was coated by a gravure roll coating method to form a coating film having a thickness of 3.0 g / m ² (dry state). Heat drying treatment was performed for 2 seconds to form a barrier resin layer. Further, a polyether polyol and an isocyanate are formed on the barrier resin layer formed above.
An anchor coating agent consisting of a 7% ethyl acetate and toluene solution of a two-part curable polyurethane resin consisting of a coating solution and a gravure roll coating method is used to form a film having a thickness of 1 μm. Coating to form an anchor coating agent layer, and then, on the surface of the anchor coating agent layer, an ethylene-α-olefin obtained by polymerization using a linear low-density polyethylene and a metallocene catalyst. Using a copolymer, each was co-extruded to a thickness of 30 μm and laminated to form a heat-sealing resin layer composed of a co-extruded film having a thickness of 60 μm. The laminated material was manufactured. Multi-layer laminated biaxially stretched film / aluminum oxide deposited film / coating thin film / barrier resin layer / anchor coat agent layer / heat-sealing resin layer -A three-sided seal-type plastic bag was produced by a filling and packaging machine, and a liquid seasoning was filled. Thereafter, the opening was heat-sealed to produce a filled and packaged product. It has a property, the deterioration of its barrier properties is not recognized, and also has excellent barrier properties against the smell of the contents and has aroma retention,
Furthermore, very good results with excellent laminating strength were obtained.

Example 3 First, a multilayer laminated biaxially stretched film composed of two types and three layers of a nylon resin layer / MXD nylon resin layer / nylon resin was manufactured by using a multilayer T-die casting method. On one nylon resin layer surface of the multi-layer laminated biaxially stretched film, a thickness of 150 was applied by chemical vapor deposition (CVD).
The multilayer film was formed by laminating two layers of the silicon oxide vapor-deposited film (2). On the other hand, as a silane coupling agent, N-β
(Aminoethyl) -γ-aminopropyltrimethoxysilane, and the silane coupling agent is 1.0% by weight.
With water: isopropyl alcohol (IPA) = 1: 1
Dissolved in 100 parts by weight of a mixed solvent consisting of
A water / alcohol-based composition containing a% wt silane coupling agent was prepared. Next, the water / alcohol prepared above
Using a silicon-based composition, two layers of the silicon oxide deposited film having a thickness of 150 ° formed as described above are layered on top of each other to form a multilayer film. −
Then, the coating was dried at 120 ° C. for 20 seconds to form a coating thin film (0.5 g / m ² , dry state) of the above-mentioned water / alcohol-based composition. next,
On the surface of the coating thin film formed above, 10 parts by weight of a barrier polyester resin was added to 90 parts by weight of a mixed solvent of toluene and methyl ethyl ketone (1: 1),
Further, 0.1 part of tolylene diisocyanate was added, and a sufficiently kneaded resin composition was used. The resin composition was coated by a gravure roll coating method to have a thickness of 3.0 g / m3. ^Two
(Dry state) to form a coating film,
The resultant was dried by heating at 30 ° C. for 30 seconds to form a barrier resin layer. Next, on the surface of the barrier resin layer formed above, an anchor coating agent comprising a 7% ethyl acetate and toluene solution of a two-part curable polyurethane resin comprising polyetherpolyol and isocyanate is applied. This was coated by a gravure roll coating method to a thickness of 1 μm to form an anchor coating agent layer.
On the coating agent layer surface, a linear low density polyethylene and an ethylene-α-olefin copolymer obtained by polymerization using a metallocene catalyst are used, and each is coextruded to a thickness of 30 μm and laminated. A heat-sealing resin layer made of a co-extruded film having a thickness of 60 μm was formed, and a laminated material according to the present invention having the following layer constitution was produced. Multi-layer laminated biaxially stretched film / two layers of silicon oxide vapor deposition / coating thin film / barrier resin layer / anchor coating agent layer / heat seal resin layer. Using the laminated material produced above, a three-sided seal-type plastic bag is produced by a die-roll filling and packaging machine, and a liquid seasoning is filled. Thereafter, the opening is heat-sealed. When a filled packaging product was manufactured, it had a high barrier property, no deterioration in the barrier property was observed, and also had excellent barrier properties against the odor of the contents and had aroma retention,
Furthermore, very good results with excellent laminating strength were obtained.

Example 4 First, on one surface of a 15 μm thick MXD biaxially stretched nylon 6 film, physical vapor deposition (PVD) was used.
Two layers of a 200 ° -thick aluminum oxide vapor-deposited film were layered to form a multilayer film. On the other hand, a polyester resin primer composition comprising a mixed solvent of toluene and methyl ethyl ketone (1: 1) containing a thermoplastic polyethylene terephthalate resin as a main component of a vehicle was prepared. next,
Using the above-mentioned polyester-based resin composition, two layers of the above-formed aluminum oxide vapor-deposited film having a thickness of 200 ° are laminated, and a multi-layer aluminum oxide vapor-deposited film is formed on the surface.
Coating is performed using a gravure roll coating method, and then dried at 100 ° C. for 5 seconds to form a coating thin film (thickness: 0.3 g /
m ² , dry). Next, 8 parts by weight of the barrier polyester resin was added to 92 parts by weight of a mixed solvent composed of toluene and ethyl acetate (1: 1) on the surface of the coating thin film formed above. A resin composition obtained by adding 0.5 part of a net and kneading it sufficiently is coated by a gravure roll coating method to have a thickness of 3.0 g / m ² (dry state). Was formed and then heated and dried at 120 ° C. for 30 seconds to form a barrier resin layer. Next, on the barrier resin layer formed as described above, an anchor coating agent comprising a 7% ethyl acetate / toluene solution of a two-component curing type polyurethane resin comprising polyester polyol and isocyanate. This is coated with a gravure roll coating method to a film thickness of 1 μm to form an anchor coating agent layer, and then a line is formed on the anchor coating agent layer surface. Low-density polyethylene and an ethylene-α-olefin copolymer obtained by polymerization using a metallocene catalyst, and coextruded to a thickness of 30 μm to obtain a thickness of 60 μm
A heat-sealing resin layer comprising a co-extruded film was formed, and a laminate according to the present invention having the following layer constitution was produced. MXD biaxially stretched nylon 6 film 2 layers of evaporated aluminum oxide film / coating thin film / barrier resin layer / anchor coating agent layer / heat seal resin layer Then, a three-sided seal-type plastic bag is manufactured by a die-roll filling and packaging machine, and at the same time, a liquid seasoning is filled. Thereafter, the opening is heat-sealed.
When filling and packaging products are manufactured, it has a high barrier property, the deterioration of the barrier property is not recognized, and it also has excellent barrier property against the odor of the contents and has aroma retention, Very good results with excellent laminate strength were obtained.

Example 5 First, the same multi-layer laminated biaxially stretched film as in Example 2 was used, and one surface thereof was subjected to chemical vapor deposition (CVD).
To form a 200 厚 thick silicon oxide deposited film,
Next, an aluminum oxide deposited film having a thickness of 200 ° is further formed on the silicon oxide deposited film by physical vapor deposition (PVD). A film was formed. Next, a primer composition containing a polyester resin was prepared in exactly the same manner as in Example 2 above.
Next, a primer composition containing the above polyester-based resin was used, and this was applied to the surface of a 200-mm-thick aluminum oxide vapor-deposited film obtained by laminating the two-layer vapor-deposited films formed above in the same manner as described above. , Coated using a gravure roll coating method, and then dried at 100 ° C. for 5 seconds.
A coating thin film (thickness 0.3 g / m ² , dry state) was formed from the above polyurethane resin composition. Next, a barrier resin layer was formed on the coated thin film surface in exactly the same manner as in Example 4, and a polyester polyol was further formed on the barrier resin layer. An anchor coating agent consisting of a 7% ethyl acetate and toluene solution of a two-part curable polyurethane resin consisting of isocyanate and a toluene solution was used to form a film having a thickness of 1 μm by a gravure roll coating method. And coat the anchor
Forming a coating agent layer, and then, on the anchor coating agent layer surface,
A linear low-density polyethylene and an ethylene-α-olefin copolymer obtained by polymerization using a metallocene catalyst are used and coextruded to a thickness of 30 μm to obtain a thickness of 60 μm.
m, a heat-sealing resin layer was formed, and a laminated material according to the present invention having the following layer constitution was produced. Multi-layer laminated biaxially stretched film, silicon oxide vapor-deposited film, aluminum oxide vapor-deposited film / coating thin film / barrier resin layer / anchor coating agent layer / heat-sealing resin layer Using a material, a three-sided seal type plastic bag is produced by a die roll filling and packaging machine, and a liquid seasoning is filled. Thereafter, the opening is heat-sealed to produce a filled packaging product. As a result, it has a high barrier property, deterioration of the barrier property is not recognized, and also has excellent barrier property against odor of the contents and has fragrance retention,
Furthermore, very good results with excellent laminating strength were obtained.

Example 6 First, the same multilayer laminated biaxially stretched film as in Example 3 above was used, and one side thereof was subjected to physical vapor deposition (PVD).
To form a 200 .ANG.-thick aluminum oxide vapor-deposited film, and then a 200 .mu.m-thick silicon oxide vapor-deposited on the aluminum oxide-deposited film by chemical vapor deposition (CVD). A film was formed, and a multilayer film was formed by laminating two vapor deposited films. On the other hand, as a silane coupling agent, γ-
Using glycidoxypropyltrimethoxysilane, 1.0% by weight of the silane coupling agent, silica powder 1.0%
% By weight, 13 to 15% by weight of a polyurethane resin, 3 to 4% by weight of nitrocellulose, 31 to 38% by weight of toluene,
A polyurethane resin composition comprising 29 to 30% by weight of methyl ethyl ketone (MEK) and 15 to 16% of isopropyl alcohol (IPA) was prepared. Next, using the polyurethane resin composition described above, the 2
In the same manner as described above, a gravure roll coat is formed on the surface of the 200-mm-thick silicon oxide vapor-deposited film obtained by laminating the vapor-deposited films of the layers.
Coating using the coating method and then at 120 ° C. for 2 hours.
After drying for 0 second, a core resin composition
A thin film (0.4 g / m ^{2 in} thickness, dry state) was formed. Next, on the coating thin film surface formed above,
A barrier resin layer is formed in exactly the same manner as in Example 1 above, and a two-part curable polyurethane resin comprising polyetherpolyol and isocyanate is further formed on the barrier resin layer. An anchor coating agent consisting of a 7% ethyl acetate and toluene solution was used, and this was coated to a film thickness of 1 μm by a gravure roll coating method to form an anchor coating agent layer. Then, on the surface of the anchor coating agent layer, a linear low-density polyethylene and an ethylene-α-olefin copolymer obtained by polymerization using a metallocene catalyst are used, each having a thickness of 30 μm. A layer of a co-extruded film having a thickness of 60 μm.
A sealable resin layer was formed, and a laminated material according to the present invention having the following layer constitution was produced. Multi-layer laminated biaxially stretched film, aluminum oxide vapor-deposited film, silicon oxide vapor-deposited film / coating thin film / barrier resin layer / anchor coating agent layer / heat-sealing resin layer Using a material, a three-sided seal-type plastic bag is produced by a die-roll filling and packaging machine, and at the same time, a liquid seasoning is filled. Thereafter, the opening is heat-sealed to produce a filled packaging product. As a result, it has a high barrier property, deterioration of the barrier property is not recognized, and also has excellent barrier property against odor of the contents and has fragrance retention,
Furthermore, very good results with excellent laminating strength were obtained.

COMPARATIVE EXAMPLE 1 A thickness of 20 formed by chemical vapor deposition (CVD)
A biaxially stretched nylon 6 film having a thickness of 15 μm and a silicon oxide film having a thickness of 200 μm having a vapor deposition film of silicon oxide having a thickness of 0 ° is coated with 7% of the same two-component curable polyurethane resin as in Example 1 above. An anchor coating agent consisting of a solution of ethyl acetate and toluene was used, and this was coated with gravure roll coating.
The coating method is applied to a film thickness of 1 μm to form an anchor.
A coating agent layer is formed, and then, on the surface of the anchor coating agent layer, a linear low-density polyethylene and an ethylene-α-olefin copolymer obtained by polymerization using a metallocene catalyst are used. A heat-sealing resin layer composed of a co-extruded film having a thickness of 60 μm and co-extruded to a thickness of 30 μm was laminated to produce a laminated material having the following layer constitution. Biaxially stretched nylon 6 film / silicon oxide vapor deposited film / anchor coating agent layer / heat-sealing resin layer A plastic bag of a mold was produced and filled with a liquid seasoning, and then the opening was heat-sealed to produce a filled packaging product.

Comparative Example 2 Thickness 20 formed by using physical vapor deposition (PVD)
15 μm thick with a deposited film of 0 ° aluminum oxide
An anchor coat consisting of a 7% ethyl acetate and toluene solution of the same two-part curable polyurethane resin as in Example 2 above, on the surface of the biaxially stretched nylon 6 film of aluminum oxide having a thickness of 200.degree. Using an agent, this is coated by a gravure roll coating method to a thickness of 1 μm to form an anchor coating agent layer, and then, on the anchor coating agent layer surface, A linear low-density polyethylene and an ethylene-α-olefin copolymer polymerized using a metallocene catalyst are used, each of which is coextruded to a thickness of 30 μm to form a coextruded film having a thickness of 60 μm. -A laminated material having the following layer constitution was manufactured by laminating the sealing resin layers. Biaxially stretched nylon 6 film / deposited film of aluminum oxide / anchor coat agent layer / heat-sealing resin layer A plastic bag of a mold was produced, and a liquid seasoning was filled. Thereafter, the opening was heat-sealed to produce a filled packaging product.

Experimental Example 1 Each of the laminates produced in Examples 1 to 6 and a packaging container
Each of the laminated materials and packaging containers produced in Comparative Examples 1 and 2 above was used. In Examples 1 to 6, the surface of the inorganic oxide vapor-deposited film, the surface of the coating thin film, and the heat-sealed material were used. For the surface of the hydrophilic resin layer and those of Comparative Examples 1 and 2, a laminate strength test and a tearing test were performed on the surface of the inorganic oxide vapor-deposited film and the surface of the heat-sealing resin layer. The above laminate strength test was performed using a peeling tester (made by Orientec Co., Ltd., model name,
Tensilon universal testing machine), sample 15mm width, peeling angle 90 °, load cell 5kgf, peeling speed 50mm
/ Min. In addition, tearing test
Make a 5mm cut in the end of the laminate, tear by hand,
The tear feeling was evaluated. The results are shown in Table 1 below.

[0049] In Table 1 above, the view of the tearing property means that ○ means tearing without resistance, and × means that the base material and the sealant layer cry apart and do not tear.

As shown in the above Table 1, the laminates of Examples 1 to 6 have remarkably high laminating strength as compared with those of Comparative Examples 1 and 2, thereby forming a coating thin film. As a result, it was found that the peel strength was improved. Also, the tearability was good. On the other hand, those of Comparative Examples 1 and 2 did not improve the laminating strength so much and were not preferred.

EXPERIMENTAL EXAMPLE 2 Further, the laminated materials produced in the above Examples 1 to 6 and
The following data were measured for the packaging containers manufactured by bag making or box making of the laminated materials manufactured in Comparative Examples 1 and 2 above. (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 Permeability This is a condition of a temperature of 40 ° C. and a humidity of 100% RH.
PERMATRAN]. The above measurement results are shown in Table 2 below.

[0052] In Table 2 above, the oxygen permeability is cm ³ / m ² / d
ay · 23 ° C. · 90% RH, and water vapor permeability is g / m ² / day · 40 ° C. · 100% RH.

As is evident from the results shown in Table 2 above, those of Examples 1 to 6 were excellent in oxygen permeability and water vapor permeability, while those of Comparative Examples 1 to 6 were excellent.
Both of the two were inferior.

EXPERIMENTAL EXAMPLE 3 Further, the laminated materials produced in the above Examples 1 to 6, and
The following data was measured for a small bag packaging container manufactured by bag-making or box-making of the laminated material manufactured in Comparative Examples 1 and 2 described above. (1). Sensory evaluation This was done by putting 10 cc of dressing (blue diso dressing) into a small pouch packaging container, sealing a 250 bag package in an aluminum foil laminated pouch, and sealing the bag.
After storage at 2 ° C. for 2 days, the aluminum foil laminated pouch was opened, and the panelists were subjected to sensory evaluation by five persons. The results of the above measurement are shown in Table 3 below.

[0055] In Table 1 above, almost no odor, 5 points, slightly odor,
Three points, which smelled considerably, were evaluated as one point, and a total of five persons was evaluated as a sensory evaluation score.

As is evident from the results shown in Table 3 above, those of Examples 1 to 6 were excellent in scent retention, whereas those of Comparative Examples 1 and 2 were all different. Was also inferior.

[0057]

As is apparent from the above description, the present invention provides a barrier nylon film, an inorganic oxide thin film, and a barrier polyester resin having toughness excellent in impact resistance, piercing resistance and the like. Focusing on a combination with a barrier resin film, etc., a silane coupling agent having organic and inorganic properties, a polyurethane-based resin having extensibility, a polyester-based resin, etc., first, on one surface of the barrier nylon film, One or two or more multilayer films of inorganic oxide thin films are provided, and further, a primer composition containing a silane coupling agent or a polyester resin, if necessary, on the inorganic oxide thin film. A barrier resin layer of a resin composition containing a barrier polyester-based resin as a main component of the vehicle is provided through a coating thin film of the primer composition, If necessary, at least a heat-sealing resin layer is laminated on the barrier resin layer surface via an anchor coat agent layer or a laminating adhesive layer to produce a laminated material, Thus, a packaging container is manufactured by using the laminated material to form a bag or a box, and then the contents, particularly liquid or viscous contents such as a liquid seasoning, are contained in the packaging container. Filled and packaged, has excellent transparency, high barrier properties against oxygen gas or water vapor, etc., and also has excellent impact resistance, puncture resistance, laminating strength, etc., and liquid or viscous contents It has the suitability of filling and packaging, and has no post-processing cracks, has extremely high post-processing suitability, and has sufficient microwave oven suitability even when the packaged product is microwaved. Articles as materials for use, especially liquid or viscous contents It is that it is capable of manufacturing a laminated material and packaging container or the like using it to have a packaging quality.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing a layer structure of a laminated material according to the present invention.

FIG. 2 is a schematic sectional view showing a layer configuration of a laminated material according to the present invention.

FIG. 3 is a schematic sectional view showing a layer structure of a laminated material according to the present invention.

FIG. 4 is a schematic sectional view showing a layer structure of a laminated material according to the present invention.

FIG. 5 is a schematic perspective view showing a configuration of a packaging container made from a bag or a box using the laminated material according to the present invention.

FIG. 6 is a schematic perspective view showing a configuration of a packaging container formed by bag making or box making using the laminated material according to the present invention.

FIG. 7 is a schematic configuration diagram illustrating an example of a roll-up type vapor deposition machine.

FIG. 8 is a schematic configuration diagram illustrating an example of a plasma chemical vapor deposition apparatus.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 barrier nylon film 2 inorganic oxide thin film 3 barrier resin layer 4 heat seal resin layer 5 coating thin film 6 anchor coat agent layer 6a laminating adhesive layer 7 seal Part A Laminated material B Laminated material C Laminated material D Laminated material E Three-way seal type flexible packaging container F Two-side seal type flexible packaging container

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C23C 16/40 C23C 16/40 (72) Inventor Hideaki Takahashi 1-1-1, Ichigaya-Kagacho, Shinjuku-ku, Tokyo No. Dai Nippon Printing Co., Ltd. (72) Inventor Mitsunori Tsuzuki 1-1-1, Ichigaya Kagacho, Shinjuku-ku, Tokyo Dainippon Printing Co., Ltd. (72) Inventor Hiroshi Yamamoto 1-1, Ichigaga-cho, Shinjuku-ku, Tokyo No. 1 Dai Nippon Printing Co., Ltd. F-term (reference) 3E086 AD01 BA04 BA15 BA24 BA33 BA40 BB02 BB05 BB15 BB22 CA01 4F100 AA01E AA17B AA17C AA19B AA19C AA20B AA20C AH02E AH06E AK41GAKA AK41GAKA AK41D AK41D AL05D AL05E AL06D AR00E AS00E BA05 BA07 BA10A BA10E BA26 CB03E DA01 EH66B EH66C EJ38A EJ65E EJ67E GB16 JA05D JA07D JC00 JD02A JD02D JD03 JD04 JK08E JK09 JL01 JL11E JM02B JM02C JM02E JN01 YY00D YY00E 4K029 AA11 AA25 BA43 BA44 BA46 BB02 BB10 BC00 BD00 CA01 CA03 CA05 FA07 GA03 4K030 AA06 AA09 AA14 BA42 BA43 FA01 LA12 BB05 LA12

Claims (20)

[Claims] 1. One or two or more multilayer films of inorganic oxide thin films are provided on one surface of a barrier nylon film, and a barrier polyester resin is further formed on the inorganic oxide thin film. A barrier resin layer of a resin composition containing as a main component of a vehicle, and further, on the barrier resin layer, at least a heat seal resin layer is provided. Laminated material. 2. The laminate according to claim 1, wherein the barrier nylon film is a biaxially stretched barrier nylon film. 3. A barrier nylon film comprising an MXD nylon film, a multilayer laminated film comprising a nylon resin layer, an MXD nylon resin layer and a nylon resin layer, or a nylon resin layer and an ethylene-vinyl alcohol copolymer layer. The laminated material according to claim 1, comprising a multilayer laminated film including a nylon resin layer. 4. The laminate according to claim 1, wherein the inorganic oxide thin film is composed of one or more layers of an inorganic oxide vapor-deposited film. 5. The laminate according to claim 1, wherein the inorganic oxide thin film comprises one or more layers of an inorganic oxide vapor-deposited film formed by physical vapor deposition. . 6. The laminate according to claim 1, wherein the inorganic oxide thin film comprises one or more layers of a vapor deposited inorganic oxide film formed by a chemical vapor deposition method. . 7. The method according to claim 1, wherein the inorganic oxide thin film comprises at least two layers of an inorganic oxide vapor-deposited film formed by physical vapor deposition and chemical vapor deposition. Laminated material. 8. The laminated material according to claim 1, wherein the deposited film of the inorganic oxide comprises a deposited film of silicon oxide or aluminum oxide. 9. The barrier polyester resin comprises polycondensation of ethylene glycol and terephthalic acid, and further comprises a part of the ethylene glycol component and terephthalic acid component modified with adipic acid and isophthalic acid. The laminate according to any one of claims 1 to 8, wherein the laminate is made of a modified polyester resin which has been polycondensed. 10. The barrier polyester resin according to claim 1, wherein the glass transition point is in the range of 0 ° C. to 80 ° C., and the molecular weight is in the range of 1,000 to 30,000. The laminated material described in 1 to 9. 11. The barrier polyester resin according to claim 1, wherein the glass transition point is in the range of 45 ° C. to 75 ° C., and the molecular weight is in the range of 10,000 to 25,000. The laminated material described in 1 to 10. 12. The method according to claim 12, wherein the resin composition is a polyfunctional isocyanate.
12. A method according to any one of claims 1 to 11, wherein
The laminated material described in. 13. The barrier resin layer has a thickness of 1 to 10 g.
/ M < ² > (dry state). 14. A coating thin film comprising a primer composition containing a silane coupling agent or a primer composition containing a polyester resin is provided between the inorganic oxide thin film and the barrier resin layer. The laminate according to any one of claims 1 to 13, wherein: 15. The laminated material according to claim 14, wherein the primer composition containing a silane coupling agent comprises a polyurethane resin composition containing a silane coupling agent and a filler. 16. A primer composition containing a silane coupling agent, comprising a water / alcohol containing a silane coupling agent.
15. The above-mentioned claim 14, wherein the composition comprises a toluene-based composition.
The laminated material described in. 17. The method according to claim 1, wherein an anchor coat layer or a laminating adhesive layer is provided between the barrier resin layer and the heat-sealing resin layer. ~ 16
The laminated material described in. 18. A laminating adhesive layer comprising a laminating adhesive layer formed by a curing reaction between a polyester polyol or a polyetherpolyol and a polyfunctional isocyanate. A laminate according to claim 17 characterized by the above-mentioned. 19. The adhesive layer for a laminate according to JIS K
23 ° C, 50% RH with No. 4 dumbbell according to 6301
300 mm / min. 19. The laminate according to claim 18, wherein the laminate has a tensile elongation of 300% to 550% as measured under the following conditions. 20. One or two or more multilayer films of inorganic oxide thin films are provided on one surface of a barrier nylon film, and a barrier polyester resin is further formed on the inorganic oxide thin film. A barrier resin layer made of a resin composition containing as a main component of a vehicle, and further, on the barrier resin layer, at least a laminated material having a heat-sealing resin layer laminated thereon is used. A packaging container characterized by being made into a bag or a box.