JP2000263725A - 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: A barrier resin layer 2 comprising a resin compsn. containing a polyvinyl alcohol resin as a main component of a vehicle is provided on one surface of a barrier nylon film l and one layer of an inorg. oxide membrane or a multilayered film of two or more membranes 3 is provided on the other surface thereof and a coating membrane 4 comprising a silane coupling agent- containing a primer compsn. or a polyester resin compsn. is provided on the layer of one or more inorg. oxide membrane 3 and at least a heat-sealable resin layer 5 is laminated to the coating membrane.

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 laminating material constituting the bag body lacks laminating strength under the influence of the content, There is a problem that a separation phenomenon or the like is caused between the layers, and that it is not necessary. 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 the above-mentioned liquid seasoning is filled and broadcasted, a film using a nylon film or the like as a base film on which an inorganic oxide vapor-deposited film is provided is compared with a film using a polyethylene terephthalate film, There is a problem that the fragrance retention and the like are inferior due to the difference in the fragrance retention and the like of the base film. Further, in the above case, on the inorganic oxide deposited film, further,
A transparent barrier film in which a gas barrier coating with a sol-gel coating agent having a metal alkoxide compound or a hydrolyzate thereof as a main component has been proposed,
The fact that a film using a nylon film or the like as a base film cannot solve the problem of inferior fragrance retention and the like as compared with a film using a polyethylene terephthalate film or the like is a reality. It is. In view of the above circumstances, the present invention has excellent transparency and high barrier properties against oxygen gas, water vapor, and the like, and further has fragrance retention, impact resistance, piercing resistance, and storage for contents. Provided is a laminated material which is rich in properties, has good post-processing suitability, has excellent laminating strength, and has good filling and packaging suitability for contents, particularly liquid seasonings, and a packaging container using the same. It is intended to do so.

[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. A combination of a tough biaxially stretched barrier nylon film, a thin film of inorganic oxide and a barrier resin layer of a polyvinyl alcohol-based resin, an organic and inorganic silane coupling agent, Focusing on polyurethane-based resins, polyester-based resins, etc. having, thus, on one side of the barrier nylon film,
A barrier resin layer of a resin composition containing a polyvinyl alcohol-based resin as a main component of the vehicle is provided, and one or two or more multilayer films of inorganic oxide thin films are provided on the other surface. On the above-mentioned inorganic oxide thin film, a coating thin film of a primer composition containing a silane coupling agent or a primer composition containing a polyester resin is provided, and further, on the coating thin film. , At least a heat-sealing resin layer is laminated to form a laminated material, and then the laminated material is used to make a bag or a box to produce a packaging container. When the contents, especially liquid or viscous contents such as liquid seasonings, are filled and packaged in a container, they have excellent transparency and a high barrier property against oxygen gas or water vapor, and further, have a fragrance retention property. , Impact resistant, thrust resistant It has excellent removability, laminating strength, etc., and has excellent preservability for liquid or viscous contents such as liquid seasonings, and has no post-processing cracks and has extremely high post-processing suitability. Furthermore, even if the packaged product is microwaved, it is possible to produce a laminated material having sufficient microwaveability and filling suitability for various articles as a packaging material, and a packaging container using the same. Thus, the present invention has been completed.

That is, according to the present invention, a barrier resin layer of a resin composition containing a polyvinyl alcohol-based resin as a main component of a vehicle is provided on one surface of a barrier nylon film, and an inorganic resin film is provided on the other surface. One or more multilayer films of oxide thin films are provided, and a primer composition containing a silane coupling agent or a primer composition containing a polyester-based resin is further formed on the inorganic oxide thin film. The present invention relates to a laminated material comprising a coating thin film provided thereon, and at least a heat-sealing resin layer laminated on the coating thin film, and a packaging container using the same. is there.

[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 configuration of a packaging container using the same will be described with reference to the drawings by exemplifying a few examples. FIG. 1 and FIG. FIG.
FIGS. 3 and 4 are schematic perspective views showing the configuration of a packaging container made from a bag or a box using the above-mentioned laminated material according to the present invention.

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, a barrier made of a resin composition containing a polyvinyl alcohol-based resin as a main component of a vehicle. The inorganic resin layer 2 is provided, and one or two or more multilayer films (not shown) of the inorganic oxide thin film 3 are provided on the other surface. And a primer containing a silane coupling agent.
A coating thin film 4 made of a composition or a primer composition containing a polyester resin is provided.
The basic structure is such that at least a heat-sealing resin layer 5 is laminated on the thin film 4. Further, as another example of the laminated material according to the present invention, as shown in FIG. 2, in the laminated material A shown in FIG. 1, the coating thin film 4 and the heat-sealing resin layer 5 are used. And an anchor coating agent layer 6, or
At least a heat sink is provided via the laminating adhesive layer 6a.
A laminate B obtained by laminating the sealable resin layer 5 can be given. 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, although not shown in the present invention, In addition to the heat-sealing resin layer,
Furthermore, the purpose of use, the contents to be filled and packaged, the distribution channel,
Depending on the sales form, application, and the like, other base materials can be arbitrarily laminated to design and manufacture various forms of laminated materials. In the present invention, a thin film of an inorganic oxide, a coating film of a primer composition containing a silane coupling agent or a primer composition containing a polyester-based resin, and an anchor coating agent layer, or It is important that the adhesive layer for laminating is laminated adjacent to each other in this order in order to achieve the function and effect such as close adhesion, but other base materials are used in the Depending on the purpose, application, etc., the laminate can be arbitrarily laminated to design and manufacture laminated materials of various forms. Further, in the present invention, a barrier resin layer 2, an inorganic oxide thin film 3, a coating thin film 4,
Alternatively, as a step of providing the heat-sealing resin layer 5 or the like, for example, the inorganic oxide thin film 3, the coating thin film 4, the heat-sealing resin layer 5, A step of providing the barrier resin layer 2 in this order, or a step of forming the inorganic oxide thin film 3, the coating thin film 4, the barrier resin layer 2, and the heat-sealing resin layer 5 on the barrier nylon film 1. And a barrier resin layer 2, an inorganic oxide thin film 3, a coating thin film 4, and a heat-sealing resin layer 5 on the barrier nylon film 1.
It can be manufactured through an arbitrary step such as a step of providing in this order, and others.

Next, in the present invention, the structure of the packaging container according to the present invention, which is made by making a bag or making a box using the above-described laminated material, 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 5 and 5 are superimposed on each other, and thereafter, three sides of the outer peripheral edge are heat-sealed to form seal portions 7, 7, 7 to thereby provide the present invention. The flexible packaging container C of the three-way seal type can be manufactured. Thus, in the above-mentioned three-way seal type flexible packaging container C, the contents are filled from the opening above it, and then the opening is heat-sealed to obtain various types of packaging. 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. 4, the above-mentioned laminated material A shown in FIG. The heat-sealing resin layers 5 and 5 are overlapped with the surfaces thereof facing 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 D according to the present invention can be manufactured. Thus, in the above two-way seal type soft packaging container D, the contents are filled from the opening above the soft packing container D, and then, 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, and the manufacturing method thereof will be described. Can be adopted. First, in the present invention, the laminate nylon film 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, puncture resistance and the like. Excellent, tough,
Further, any polyamide-based resin film or sheet capable of holding a thin film of an inorganic oxide can be used. Specifically, for example, MXD nylon 6 film, MXD nylon resin and nylon 46, nylon 6, nylon 66, nylon 610, nylon 6
12, a multilayer laminated film composed of two or more layers of various polyamide resins such as nylon 11, nylon 12, and the like, or an ethylene-vinyl alcohol copolymer and the above nylon 46, nylon 6, nylon 6
6, nylon 610, nylon 612, nylon 11,
A multilayer laminated film composed of two or more layers of various polyamide resins such as nylon 12 and others can be used. Thus, the above-mentioned MXD nylon 6 film or multi-layer laminated film is obtained by a conventional biaxial stretching method such as a tenter method or a tuber method.
It is desirable to use a biaxially stretched barrier nylon film stretched in the axial direction, and the thickness thereof is about 10 to 200 μm, preferably 10 to 50 μm.
Position is desirable. Also, the above MXD nylon film,
Alternatively, the multilayer laminated film may be provided with an anchor if necessary.
A surface smoothing treatment coated with a coating agent or the like, or an arbitrary pretreatment such as a corona discharge treatment, a plasma discharge treatment, a flame treatment, an ozone treatment, or the like can 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 Multilayer laminated film consisting of three types and 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
It can be used to produce a multilayer laminated film composed of three types of layers, a multilayer laminated film composed of two types and three layers, such as a nylon resin layer / MXD nylon 6 resin layer / nylon resin layer. Next, in the present invention, 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
About 200 μm, preferably about 5 to 100 μm, and an ethylene-vinyl alcohol copolymer layer,
Alternatively, as the MXD nylon resin layer, about 1 to 10
About 0 μm, preferably about 5 to 50 μm. Further, as an adhesive resin layer between each layer, about 1 to 100 μm
And preferably about 5 to 50 μm. In the above, as the ethylene-vinyl alcohol copolymer film, for example, the content of vinyl acetate is about 79 to 92 watts.
It is possible to use an ethylene-vinyl alcohol copolymer having an ethylene content of about 25 to 50 mol% obtained by completely saponifying an ethylene-vinyl acetate copolymer of t%.

Next, in the present invention, a barrier resin layer made of a resin composition containing a polyvinyl alcohol-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 barrier resin layer, first, for example, one or more polyvinyl alcohol-based resins are used as a main component of the vehicle, and
Further, if necessary, for example, fillers, stabilizers, plasticizers,
Add optional additives such as light stabilizers such as antioxidants and ultraviolet absorbers, dispersants, thickeners, drying agents, lubricants, antistatic agents, crosslinking agents, etc. A resin composition composed of a solvent type, an aqueous type, an emulsion type, or the like kneaded into the mixture is prepared. Thus, in the present invention, the above resin composition is used, for example, a roll coat method, a gravure roll coat method, a kiss roll coat method, a squeeze roll coat method, Coating amount, for example, 0.1 g / m ^{2 to} 20 g, by a coating method such as a reverse roll coating method, a curtain flow coating method, or the like.
/ M ² (dry state), preferably 0.5 g / m ² to
Coating is performed so as to be about 10 g / m ² (dry state), followed by heat drying and further aging treatment to form the barrier resin layer according to the present invention. As the above-mentioned resin composition, a polyvinyl alcohol-based resin is dissolved or kneaded, and further, since these are cured, it is possible to use a resin composition prepared using an alcohol-water-based solution or the like. Preferably, the alcohol component includes, for example, n-propyl alcohol, isopropyl alcohol, n-butanol,
t-Butanol, ethyl alcohol, methyl alcohol and the like can be used. In the above-mentioned alcohol-water solution, the mixing ratio of alcohol to water is, for example, alcohol- , 50 to 70 parts by weight of water,
It is desirable to prepare an alcohol-water solution by mixing 50 to 30 parts by weight.

In the above, as the polyvinyl alcohol-based resin, for example, a water-soluble polyvinyl alcohol resin obtained by saponifying polyvinyl acetate can be used. Further, in the above, as the polyvinyl alcohol-based resin, for example, the content of vinyl acetate is 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.
The above-mentioned polyvinyl alcohol-based resin or ethylene-vinyl alcohol copolymer has high gas barrier properties, and is also excellent in fragrance retention, transparency and the like. Thus, in the above ethylene-vinyl alcohol copolymer, those having an ethylene content of 50 mol% or more are not preferred because the oxygen gas barrier properties are sharply reduced and the transparency is also deteriorated. Further, those having a content of 25 mol% or less are not preferred because the thin film becomes brittle and the oxygen gas barrier property is reduced under high humidity.

In the above resin composition, the additive
Specifically, polyvinyl alcohol resin,
Or the ethylene-vinyl alcohol copolymer has
Reacts with hydroxyl, etc., and reacts with the polyvinyl alcohol
Fat or ethylene-vinyl alcohol copolymer
Connect molecules to each other with chemical bonds to form a three-dimensional network
Polyfunctional compounds that can constitute (cured) polymer compounds
Can be used. As the above polyfunctional compound
Is, for example, tetramethoxysilane, tetraethoxyc
Alkoxy silanization of Lante, tetrabutoxy silane, etc.
Compound, tetramethoxyzirconium, tetraethoxydi
Zirconium alkoxide compounds such as ruconium, tet
Lamethoxy titanium, tetraethoxy titanium titanium
Metal alkoxide compounds such as alkoxide compounds
And / or its hydrolyzate can be used
You. Further, in the present invention, the above polyfunctional compound
Thus, for example, -CH = CH _TwoGroup, = C = O group, -C≡N
Reacts with active hydrogen such as epoxy group, epoxy group and ethyleneimine group
Having a functional group, -OH group, -SH group, -C
OOH group, -NH_TwoCompounds having active hydrogen such as
And compounds having a halogen group, salt, chelate-forming group, etc.
A cross-linking agent composed of a substance or the like can be used. Specifically
Are, for example, dialdehyde compounds, dicarboxylic oxidation compounds
Compounds, diimide compounds, di- or polyhydric alcohol compounds,
Diamine compounds, diisocyanate compounds, bisepoxy
Compound, bisethyleneimine compound, divinyl compound
Products, zirconium compounds, titanium chelate compounds,
Others and the like can be used.

Further, in the present invention, a silane coupling agent having a binary reactivity can be used as the above-mentioned polyfunctional compound. Examples of the silane coupling agent include 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-aminopropyltrimethoxy Silane, N-β
(Aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane,
Bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane, one of γ-aminopropylsilicone
Seeds or more can be used. Only a small amount may be used. In the present invention, a polyvinyl alcohol resin, or a hydroxyl group or the like of an ethylene-vinyl alcohol copolymer and the above-mentioned metal alkoxide compound, a cross-linking agent, a silane coupling agent and the like react to form a cross-linked structure. When constructing
For example, a curing catalyst or the like can be added. Examples of the above-mentioned curing catalyst include, for example, tertiary amines which are substantially insoluble in water and soluble in an organic solvent. N-
Dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine and the like, and as the acids, for example, mineral acids such as sulfuric acid, hydrochloric acid and nitric acid, and organic acids such as acetic acid and tartaric acid can be used. It is sufficient to add a small amount as the amount used.

In the present invention, the above-mentioned polyvinyl alcohol-based resin is used as a main component of the vehicle, and if necessary, an additive is optionally added thereto to form an alcohol-based resin.
Prepare a resin composition which is sufficiently kneaded with an aqueous solvent, diluent, etc., coat it with a usual coating method, and then apply heat drying and further aging treatment. The barrier resin layer formed by the above is excellent in tight adhesion with the barrier nylon film, the adhesive strength between the two is extremely strong, and a phenomenon such as peeling between the layers is not recognized.Moreover, in the present invention, The two layers of the inorganic oxide thin film and the above-mentioned barrier resin layer synergistically constitute a barrier film, thereby significantly improving the barrier properties against oxygen gas, water vapor gas and the like, and exhibiting transparency, It is excellent in heat resistance, hot water resistance, laminating suitability, etc., and can produce an extremely good laminated material.

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 basically comprises a metal oxide. Any thin film that has been made amorphous can be used. For example, silicon (Si), aluminum (Al), magnesium (Mg), calcium (C)
a), potassium (K), tin (Sn), sodium (N
a) A thin film in which an oxide of a metal such as boron (B), titanium (Ti), lead (Pb), zirconium (Zr), and yttrium (Y) is made amorphous can be used. Thus, as a material suitable for a packaging material or the like, a thin film in which an oxide of a metal such as silicon (Si) or aluminum (Al) is made amorphous can be given. 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 , Al
O _X, MO _X (However, as such as MgO _X, in the formula, M
Represents a metal element, and the range of the value of X differs depending on the metal element. ). Further, as the range of the value of X, silicon (Si) is 0 to 2, aluminum (Al) is 0 to 1.5, 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, and boron ( B) is 0 to
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, as the inorganic oxide thin film, one layer of the inorganic oxide thin film as described above,
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 of forming a multilayer film having one or two or more inorganic oxide thin films is shown in FIG. 5. FIG. 5 shows an example of a roll-up type vacuum evaporator. It is a schematic block diagram. As shown in FIG. 5, in the vacuum chamber 111, the barrier nylon film 113 unwound from the unwinding 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, if necessary, oxygen or the like is blown out from the oxygen blow-out port 117, on the above-mentioned barrier nylon film 113 on the cooled coating drum 114.
Forming a vapor-deposited film of an inorganic oxide through the masks 118, 118, and then sending out the barrier nylon film 113 on which the vapor-deposited film is formed into the vacuum chamber 111; The barrier nylon film 11 having an inorganic oxide thin film
3 can be manufactured. Thus, in the present invention, the above-mentioned film formation is repeated, or, although not shown, the above-mentioned winding type vacuum evaporator is connected in two or more to continuously evaporate. By doing so, an inorganic oxide thin film comprising two or more multilayer films of inorganic oxide thin films can be formed.

Further, in the present invention, a specific example of a film formation method in which an inorganic oxide thin film is laminated in two or more layers by the above-described plasma chemical vapor deposition method is shown in 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 for forming a multilayer film having 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. Method (Physical Vap
or Deposition method, PVD method) and chemical vapor deposition methods such as plasma-enhanced chemical vapor deposition, thermal chemical vapor deposition, and photochemical vapor deposition.
Deposition method, CVD method), and by forming an inorganic oxide thin film composed of both layers into two or more layers to form a film, an inorganic oxide thin film composed of two or more inorganic oxide thin films is formed. Oxide thin films can also be manufactured. That is, although not shown, first, a first inorganic oxide thin film is formed using the above-mentioned roll-up type vacuum evaporator, and then the above-described plasma chemical vapor deposition is performed on the inorganic oxide thin film. A second inorganic oxide thin film is formed using the apparatus, and the first and second inorganic oxide thin films are used to form 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 may be performed using a roll-to-roll vacuum evaporator, and then film formation may be performed using a plasma chemical vapor deposition apparatus. May be used to form a film.

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 coating thin film of a primer composition containing a silane coupling agent, which constitutes the container for packaging a laminate according to the present invention, will be described. As the primer composition containing, 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 can be used. it can. 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-aminopropylsilico-
One or more kinds of aqueous solutions of olefins can be used. The silane coupling agent as described above hydrolyzes a functional group at one end of the molecule, usually, a chloro, alkoxy, or acetoxy group, and a silanol group (Si).
OH), which forms a metal constituting the thin film of the inorganic oxide, 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 any action, for example, a dehydration condensation reaction or the like. A reaction occurs, and the silane coupling agent is modified on the surface of the inorganic oxide thin film by a covalent bond or the like. Further, a strong bond is formed on the surface of the inorganic oxide thin film of the silanol group itself by adsorption or hydrogen bonding. Form. 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, an adhesive layer for laminating Reacts with substances constituting the anchor coating agent layer and other layers to form a strong bond. Thus, in the present invention, the inorganic oxide thin film and the heat seal property are bonded to each other through the laminating adhesive layer, the anchor coating agent layer, and the like by the chemical bonding as described above. The resin layer is firmly and tightly adhered, thereby increasing the laminating strength and enabling a strong laminated structure having a high laminating strength to be formed. In the present invention, the inorganic and organic properties of the silane coupling agent are utilized, and the heat transfer is performed through a thin film of an inorganic oxide and a laminating adhesive layer or an anchor coating agent layer. To improve the tight adhesion with the resin layer, thereby increasing the laminate strength and the like.

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
%, Filler 0.1-20% by weight, preferably 1-1
It is added at a ratio of about 0% by weight, and 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. The polyurethane resin composition is prepared by mixing well. 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,
Through a laminating adhesive layer, an anchor coating agent layer, etc., the inorganic oxide thin film and the heat-sealing resin layer are firmly and closely adhered to each other, and the laminating strength is increased. This makes it possible to form a strong laminated structure having high laminate strength.
Furthermore, in the present invention, utilizing the inorganic and organic properties of the silane coupling agent, a heat seal is provided via an inorganic oxide thin film and an adhesive layer or an anchor coat agent layer. This improves the tight adhesion with the conductive resin layer, thereby increasing the laminate strength and the like.

Next, in the present invention, a coating thin film made of a primer composition containing a polyester resin constituting a laminate according to the present invention will be described. As the polyester resin, for example, terephthalic acid or the like is used. A thermoplastic polyester resin formed by polycondensation of one or more aromatic saturated dicarboxylic acids having a benzene nucleus as a basic skeleton with one or more saturated divalent alcohols can be used. . In the above, examples of the aromatic saturated dicarboxylic acid having a benzene nucleus as a basic skeleton include terephthalic acid, isophthalic acid, phthalic acid, diphenyl ether-4, 4-dicarboxylic acid,
Others can be used. In the above, the saturated divalent alcohol may be ethylene glycol-
Propylene glycol, trimethylene glycol,
Tetramethylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, hexamethylene glycol
, Dodecamethylene glycol, neopentyl glyco-
Aliphatic glycols such as cyclohexanedimethanol, alicyclic glycols such as cyclohexanedimethanol, 2.2-bis (4 '-. Beta.-hydroxyethoxyphenyl) propane, naphthalenediol
And other aromatic geo- and the like.
In the present invention, as the polyester-based resin, specifically, for example, a thermoplastic polyethylene terephthalate resin formed by polycondensation of terephthalic acid and ethylene glycol, or a mixture of terephthalic acid and tetramethylene glycol Thermoplastic polybutylene terephthalate resin formed by polycondensation, thermoplastic polycyclohexane dimethylene terephthalate resin formed by polycondensation of terephthalic acid and 1,4-cyclohexanedimethanol, terephthalic acid and isophthalic acid Thermoplastic polyethylene terephthalate resin formed by copolycondensation of acid and ethylene glycol, thermoplasticity formed by copolycondensation of terephthalic acid with ethylene glycol and 1,4-cyclohexanedimethanol Polyethylene terephthalate resin, terephthalic acid and isophthalic acid Renguriko - Le and propylene glycol - thermoplastic polyethylene terephthalate produced by co-polycondensation of Le - DOO resins, polyester polyol - Le resin,
Others can be used. In the present invention, the above-described 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 kinds of aliphatic saturated dicarboxylic acids such as dodecanoic acid can be added for copolycondensation, and the amount used is based on the amount of aromatic saturated dicarboxylic acid having a benzene nucleus as a basic skeleton. 1 to
It is preferable to add about 10% by weight for use.

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 primer composition containing a polyester resin, for example,
It is preferably about 0.01 to 50 μm, and more preferably about 0.1 to 5 μm. In the present invention, in particular, the close adhesion between the inorganic oxide thin film and the heat-sealing resin layer is improved by the coating thin film of the primer composition containing the polyester resin as described above. As a matter of course, it acts as a primer layer, and further has the advantage of improving the fragrance retention and the like of the contents in a packaging container using the laminated material. In the present invention, as the polyester-based resin constituting the coating film of the primer composition containing the polyester-based resin as described above, particularly, among the polyester-based resins described above, a polyester polyol-based resin is used. Is preferred.

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, as the resin of the ethylene / α-olefin copolymer polymerized by using the above-mentioned metallocene catalyst, a film or sheet or a composition containing the copolymer is used. -It can be used in the form of a coating film or the like, thereby functioning as a heat-sealing resin film or sheet constituting the innermost layer, and thus its low-temperature heat sheet. This makes it possible to prevent the occurrence of cracks or the like occurring in the inorganic oxide thin film or the like during post-processing such as bag making. The thickness of the film or film or sheet is about 3 μm to 300 μm, preferably
5 μm to 100 μm 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, a partially crosslinked ethylene-propylene rubber (EPDM),
Ethylene-propylene rubber (EPR), styrene-butadiene-styrene block copolymer (SBS), styrene-isobutylene-styrene block copolymer
(SIS), using a heat-sealing resin layer of a resin composition obtained by adding one or more thermoplastic elastomers such as styrene-ethylene-butylene-styrene block copolymer (SEBS). Can also. In the present invention, as the heat-sealing resin layer,
For example, a heat-sealing property comprising a multilayer structure obtained by co-extruding a linear low-density polyethylene and an ethylene-α-olefin copolymer obtained by polymerization using a metallocene catalyst. It may be a resin layer.

Next, in the present invention, as a method of laminating the above-mentioned heat-sealing resin layer on the above-mentioned coated thin film surface, for example, a laminating adhesive with a laminating adhesive is used. It can be performed by a dry lamination method of laminating via an agent layer or an extrusion lamination method of laminating via a melt-extruded resin layer of a melt-extruded adhesive resin. In the above, as the adhesive for laminating, for example, a one-component or two-component curing or non-curing type vinyl, (meth) acrylic,
Polyamide, polyester, polyether, polyurethane, epoxy, rubber, and other solvent types,
An aqueous adhesive or an emulsion adhesive such as an emulsion adhesive can be used. Thus, the above lamine
Examples of the coating method of the adhesive for coating include a direct gravure coating method, a gravure coating method, a kiss coating method, a reverse coating method, a fonten method, and a transfer coating method. -Can be applied by a method such as a coating method or the like, and the coating amount is as follows:
It is preferably about 0.1 to 10 g / m ² (dry state), more preferably about 1 to 6 g / m ² (dry state). In addition,
In the present invention, an adhesion promoter such as a silane coupling agent can be optionally added to the above-mentioned adhesive for laminating. Next, in the above description, as the melt-extruded adhesive resin, the above-mentioned thermoplastic resin forming the thermoplastic resin layer can be similarly used. Thus, in the present invention, it is preferable to use a low-density polyethylene, particularly a linear low-density polyethylene, and an acid-modified polyethylene, as the melt-extruded adhesive resin. The thickness of the melt-extruded resin layer of the melt-extruded adhesive resin is about 5 to 100 μm,
More preferably, about 10 to 50 μm is desirable. In addition,
In the present invention, when it is necessary to obtain a stronger adhesive strength when performing lamination by the extrusion lamination method, for example, an anchor may be provided on the surface of the coating thin film.
An adhesion improver such as a coating agent may be coated.
As the above-mentioned anchor coating agent, specifically, for example, an organic titanium-based anchor coating such as alkyl titanate is used.
Water-based or oil-based anchor coating agents such as a coating agent, an isocyanate anchor coating agent, a polyethyleneimine anchor coating agent, a polybutadiene anchor coating agent, and the like. Can be used. Thus, in the present invention, the above-mentioned anchor coating agent can be used, for example, by roll coating, gravure coating, knife coating, dip coating, spray coating, and other coating methods. In-
And dry the solvent, diluent, etc.
The agent layer can be formed. In the above, the coating amount of the anchor coating agent is desirably about 0.1 to 5 g / m ² (dry state).

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 synergistic with that of the above-mentioned coating thin film and the like, and the inorganic oxide thin film, the coating thin film and the laminating material constituting the laminated material are laminated. The purpose of the present invention is to improve the tight adhesion with an adhesive layer, a heat-sealing resin layer and the like, thereby preventing the occurrence of cracks in the inorganic oxide thin film. In the above, if the tensile elongation is less than 300%, it lacks flexibility, and
In the post-processing such as bag making or box making, cracks and the like are generated in the inorganic oxide thin film, and when the tensile elongation exceeds 550%, the flexibility becomes excessive and the tearing property becomes excessive. This is not preferable because, for example, 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 one surface of a biaxially stretched MXD 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. Then
N-β (aminoethyl) as a silane coupling agent
Using -γ-aminopropyltrimethoxysilane, 1.0% by weight of the silane coupling agent,
% 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 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. , 1
The coating was dried at 00 ° C. for 5 seconds to form a coating thin film (0.4 g / m ^{2 in} a dry state) of the above-mentioned polyurethane resin composition. On the other hand, on the other surface of the biaxially stretched MXD nylon 6 film having a thickness of 15 μm, ion-exchanged water of ethylene-vinyl alcohol copolymer (ethylene content: 32 mol%) and n-propyl alcohol (1 /
1) A resin composition consisting of 100 parts by weight of a 15% solution in a solvent was used, and this was coated by a gravure roll coating method.
To a 1.1 g / m ² (dry state) core
Then, a heat treatment was performed at 120 ° C. for 5 minutes to form a barrier resin layer. Next, a 7% ethyl acetate and toluene solution of a two-part curable polyurethane resin composed of polyester polyol and isocyanate is formed on the coated thin film surface of the polyurethane resin composition formed above. An anchor coating agent is used, and is coated to a film thickness of 1 μm by a gravure roll coating method to form an anchor coating agent layer, and then the anchor coating agent is formed. On the agent layer surface, a linear low-density polyethylene and ethylene-α polymerized using a metallocene catalyst
Using an olefin, each of which is 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. The laminated material was manufactured. Barrier resin layer / Biaxially stretched MXD nylon 6 film
Silicon oxide deposited film / coating thin film / anchor coating agent layer / heat-sealing resin layer Next, using the laminated material produced above, a three-way sealing is performed by a die roll filling and packaging machine. A plastic bag was manufactured and filled with a liquid seasoning, and then the opening was heat-sealed to produce a filled and packaged product. No deterioration was observed, and the content was excellent in fragrance retention and the like, and further, excellent results were obtained 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 comprising three types and five layers of an adhesive resin layer / a nylon resin layer is produced, and then, physical vapor deposition (PVD) is applied to one surface of the multilayer laminated biaxially stretched film. Use, thickness 200
An aluminum oxide vapor-deposited film was formed. On the other hand, a polyester resin composition containing a thermoplastic polyethylene terephthalate resin as a main component of the vehicle was prepared. next,
Using the polyester resin composition described above, on the surface of the deposited film of aluminum oxide having a thickness of 200 ° formed above,
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). On the other hand, 10 parts by weight of an ethylene-vinyl alcohol copolymer (ethylene content: 32 mol%), 34 parts by weight of tetraethoxysilane, 15 parts by weight of water,
An aqueous resin composition consisting of 10 parts by weight of isopropyl alcohol, 0.17 parts by weight of a tertiary amine catalyst, and 3.4 parts by weight of epoxysilane was used.
0.9g / m thickness by coating
² (dry state) coating film is formed.
Heat treatment was performed at 20 ° C. for 1 minute to form a barrier resin layer.
Next, on the coated thin film surface formed above, an anchor coat composed of a 7% ethyl acetate and toluene solution of a two-part curable polyurethane resin composed of polyetherpolyol and isocyanate. Using an agent, this is coated by a gravure roll coating method 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. A low-density linear polyethylene and an ethylene-α-olefin polymerized using a metallocene catalyst, each of which is co-extruded to a thickness of 30 μm to form a heat extruded film having a thickness of 60 μm. To form a laminated material according to the present invention having the following layer constitution. Barrier resin layer / multilayer laminated biaxially stretched film / deposited film of aluminum oxide / coating thin film / anchor coating agent layer / heat-sealing resin layer Next, the laminated material produced above is used. Then, a three-sided seal-type plastic bag was produced by a die-roll filling and packaging machine, and at the same time, a liquid seasoning was filled. Thereafter, the opening was heat-sealed to produce a filled and packaged product. It has a high barrier property, no deterioration of the barrier property is recognized, and it has excellent results such as excellent fragrance retention of the contents and excellent laminate strength.

Example 3 First, using a multilayer T-die casting method, two types of nylon resin layer / MXD nylon resin layer / nylon resin layer were used.
Producing a multilayer laminated biaxially stretched film consisting of layers,
On the nylon resin layer surface of the multilayer laminated biaxially stretched film, two layers of a 150 ° -thick silicon oxide vapor-deposited film were formed by chemical vapor deposition (CVD) to form a multilayer film. On the other hand, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane was used as a silane coupling agent, and 1.0% by weight of the silane coupling agent was added to water:
A water / alcohol-based composition containing a silane coupling agent having a concentration of 1.0% by weight was dissolved in 100 parts by weight of a mixed solvent consisting of isopropyl alcohol (IPA) = 1: 1. Next, using the water / alcohol-based composition adjusted as described above, two layers of the silicon oxide deposited film having a thickness of 150 ° formed as described above are laminated to form a multilayer film on the silicon oxide deposited film surface. -Coating using a coating method, and then drying at 120 ° C for 20 seconds.
Coating thin film (thickness 0. 0) made of alcohol-based composition
5 g / m ² , dry). Next, on the coated thin film surface formed above, an anchor coat consisting of a 7% ethyl acetate and toluene solution of a two-part curable polyurethane resin consisting of polyetherpolyol and isocyanate. The coating agent was coated to a film thickness of 1 μm by a gravure roll coating method to form an anchor coat.
Forming a coating agent layer, and then, on the anchor coating agent layer surface,
A linear low-density polyethylene and an ethylene-α-olefin polymerized using a metallocene catalyst are used, each of which is co-extruded to a thickness of 30 μm to form a heat extruded film having a thickness of 60 μm. An elastic resin layer was formed. Next, 10 parts by weight of ethylene-vinyl alcohol copolymer (ethylene content 32 mol%), 34 parts by weight of tetraethoxysilane, 15 parts by weight of water, 10 parts by weight of alcohol, 0.17 parts by weight of tertiary amine catalyst,
An aqueous resin composition consisting of 3.4 parts by weight of epoxysilane was used and coated by a gravure roll coating method to form a coating film having a thickness of 0.9 g / m ² (dry state). After that, a heat treatment was performed at 120 ° C. for 1 minute to form a barrier resin layer, thereby producing a laminate according to the present invention having the following layer constitution. Barrier resin layer / multilayer laminated biaxially stretched film / silicon oxide vapor-deposited film 2 layers / coating thin film / anchor coat agent layer / heat-sealing resin layer , A three-sided seal-type plastic bag was produced by a die-roll filling and packaging machine, and a liquid seasoning was filled. Thereafter, the opening was heat-sealed to produce a filled packaging product. However, it had a high barrier property, no deterioration of the barrier property was recognized, and excellent results such as excellent fragrance retention of the contents and excellent lamination strength were obtained.

Example 4 First, on one surface of a biaxially stretched MXD nylon 6 film having a thickness of 15 μm, a physical vapor deposition (PVD) method 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 composition containing a thermoplastic polyethylene terephthalate resin as a main component of the vehicle was prepared. Next, using the above-mentioned polyester-based resin composition, the thickness of 200
In the same manner as described above, a two-layered aluminum oxide vapor-deposited film is laminated on the multi-layered aluminum oxide vapor-deposited film surface by the gravure roll coating method, and then coated at 100 ° C. for 5 hours. After drying for 2 seconds, a coating thin film (thickness of 0.3 g / m
² , dried state). Next, the core formed above
A two-component curable polyurethane resin consisting of polyester polyol and isocyanate
% Of ethyl acetate and a toluene solution, and coating the film with a gravure roll method to a thickness of 1 μm to form an anchor coat agent layer. Then, a linear low-density polyethylene and an ethylene-α-olefin polymerized using a metallocene catalyst are used on the surface of the anchor coating agent layer, and these are coextruded to a thickness of 30 μm. A heat-sealing resin layer made of a co-extruded film having a thickness of 60 μm was formed. Next, on the other surface of the biaxially stretched MXD nylon 6 film having a thickness of 15 μm, an ethylene-vinyl alcohol
Of ethylene copolymer (ethylene content 32 mol%) with ion-exchanged water and n-propyl alcohol (1/1) solvent
% Solution was added to 100 parts by weight of the resin composition and 1 part by weight of a 30% solution of zirconium acetate in the same solvent was used. The resin composition was coated by a gravure roll coating method to obtain a thickness. A coating film of 1.1 g / m ² (dry state) was formed, followed by heat treatment at 120 ° C. for 5 minutes to form a barrier resin layer. Lumber was manufactured. Barrier resin layer / Biaxially stretched MXD nylon 6 film
Two layers of deposited aluminum oxide film / coating thin film / anchor coating agent layer / heat-sealing resin layer Next, using the laminated material produced above, a three-way die-roll packing machine was used. When manufacturing a sealed plastic bag and filling it with a liquid seasoning, and then heat sealing the opening to manufacture a filled packaging product, the product has a high level of barrier properties. No deterioration of the properties was observed, the content was excellent in the fragrance retention and the like, and further, excellent results were obtained with excellent laminating strength.

Example 5 A biaxially stretched MXD nylon 6 film having a thickness of 15 μm was coated on one surface by chemical vapor deposition (CVD) to a thickness of 2 μm.
A deposited film of silicon oxide is formed on the deposited silicon oxide film by using physical vapor deposition (PVD).
Forming a 200-mm-thick aluminum oxide deposited film;
A multilayer film was formed by layering the deposited films. Next, a polyester resin composition containing thermoplastic polyethylene terephthalate resin as a main component of the vehicle was prepared. Next, using the above-mentioned polyester-based resin composition, a gravure roll coating method was applied to the surface of a 200-mm-thick aluminum oxide vapor-deposited film formed by laminating the two-layer vapor-deposited films formed above. And then dried at 100 ° C. for 5 seconds, and coated with the above-mentioned polyester resin composition.
A thin film (thickness: 0.3 g / m ² , dry state) was formed. On the other hand, on the other surface of the biaxially stretched MXD nylon 6 film having a thickness of 15 μm, ion-exchanged water of ethylene-vinyl alcohol copolymer (ethylene content: 32 mol%) and n-propyl alcohol (1 / 1) 1 with solvent
A resin composition obtained by adding 1 part by weight of a 30% solution of a carbodiimide in the same solvent to 100 parts by weight of a 5% solution is used, and the resin composition is coated by a gravure roll coating method to obtain a thickness. A coating film of 1.1 g / m ² (dry state) was formed, and then heated at 120 ° C. for 5 minutes to form a barrier resin layer. Next, a 7% ethyl acetate and toluene solution of a two-part curable polyurethane resin composed of polyester polyol and isocyanate is formed on the coated thin film surface of the polyester resin composition formed above. An anchor coating agent is used, and is coated to a film thickness of 1 μm by a gravure roll coating method to form an anchor coating agent layer.
On the surface of the anchor coating agent layer, linear low-density polyethylene and ethylene-α-polymerized using a metallocene catalyst were used.
Olefin copolymers, each having a thickness of 30
A heat-sealing resin layer composed of a co-extruded film having a thickness of 60 μm was formed by co-extrusion to a thickness of μm, and a laminated material according to the present invention having the following layer constitution was manufactured. Barrier resin layer / Biaxially stretched MXD nylon 6 film
Silicon oxide deposited film / Aluminum oxide deposited film / core
Thinning film / anchor coat 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 the liquid is seasoned. The product was filled and then the opening was heat-sealed to produce a filled packaged product. As a result, the product had a high barrier property, no deterioration of the barrier property was observed, and Excellent results such as excellent fragrance retention and laminate strength were obtained.

Example 6 First, a biaxially stretched MXD nylon 6 film having a thickness of 15 μm was applied to one surface of the film by physical vapor deposition (PVD).
A 200-mm-thick aluminum oxide deposition film is formed, and then a 200-thick-thick silicon oxide deposition film is formed on the aluminum oxide deposition film by chemical vapor deposition (CVD). And a multilayer film was formed by laminating two layers of the deposited film. Next, γ-glycidoxypropyltrimethoxysilane was used as a silane coupling agent, and the silane coupling agent was 1.0% by weight, silica powder was 1.0% by weight,
13-15% by weight of polyurethane resin, nitrocellulose
3-4% by weight, toluene 31-38% by weight, methyl ethyl ketone (MEK) 29-30% by weight, isopropyl
A polyurethane resin composition comprising 15-16% of rualcoal (IPA) was prepared. Next, using the above-mentioned polyurethane-based resin composition, the two-layered vapor-deposited film formed as described above is laminated, and a 200-mm-thick silicon oxide vapor-deposited film is formed on the multi-layered film by the gravure roll coating method. And then dried at 120 ° C. for 20 seconds to form a coating thin film (thickness: 1. 1) of a polyurethane resin composition.
0 g / m ² , dry). On a coated thin film surface of the polyurethane resin composition formed as described above, an anchor composed of a 7% ethyl acetate and toluene solution of a two-part curable polyurethane resin composed of polyetherpolyol and isocyanate. Using a coating agent, this is coated to a film thickness of 1 μm using a gravure roll coating method to form an anchor coating agent layer, and then the anchor coating is formed. On the agent layer surface, linear low-density polyethylene and ethylene-α polymerized using a metallocene catalyst
Olefin copolymers, each having a thickness of 3
It was co-extruded to a thickness of 0 μm to form a heat-sealing resin layer made of a co-extruded film having a thickness of 60 μm. Next, 10 parts by weight of an ethylene-vinyl alcohol copolymer (ethylene content: 32 mol%), 34 parts by weight of tetraethoxysilane, water were added to the other surface of the biaxially stretched MXD nylon 6 film having a thickness of 15 μm. An aqueous resin composition consisting of 15 parts by weight, 10 parts by weight of isopropyl alcohol, 0.17 parts by weight of a tertiary amine catalyst and 3.4 parts by weight of epoxysilane was used, and this was obtained by a gravure roll coating method. Coating to form a coating film having a thickness of 0.9 g / m ² (dry state), followed by heat treatment at 120 ° C. for 1 minute to form a barrier resin layer. A laminated material according to the present invention having a layer configuration was manufactured. Barrier resin layer / Biaxially stretched MXD nylon 6 film
Aluminum oxide deposited film / Silicon oxide deposited film / core
Thinning film / anchor coat 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 the liquid is seasoned. The product was filled and then the opening was heat-sealed to produce a filled packaged product. As a result, the product had a high barrier property, no deterioration of the barrier property was observed, and Excellent results such as excellent fragrance retention and laminate strength were obtained.

Example 7 In Example 1 described above, the ethylene-vinyl alcohol copolymer (ethylene content: 32 mol%) was prepared by using 15% of ion-exchanged water and n-propyl alcohol (1/1) solvent.
Instead of using the resin composition consisting of 100 parts by weight of the solution, ion-exchange water of polyvinyl alcohol resin and n-
A resin composition consisting of 100 parts by weight of a 15% solution in propyl alcohol (1/1) solvent was used.
A laminated material according to the present invention was manufactured in the same manner as in Example 1 described above. 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 the filled and packaged product was manufactured, it had a high barrier property, no deterioration of the barrier property was observed, and it was also excellent in the fragrance retention of the contents, and further, excellent in the laminate strength. Results were obtained.

Example 8 In Example 2, 10 parts by weight of an ethylene-vinyl alcohol copolymer (ethylene content: 32 mol%), 34 parts by weight of tetraethoxysilane, 15 parts by weight of water, 10 parts by weight of isopropyl alcohol Parts by weight, tertiary amine catalyst 0.17
Instead of using an aqueous resin composition consisting of 3.4 parts by weight of epoxysilane, 10 parts by weight of polyvinyl alcohol resin, 34 parts by weight of tetraethoxysilane, 15 parts by weight of water, 10 parts by weight of isopropyl alcohol Using an aqueous resin composition comprising 0.1 parts by weight of a tertiary amine catalyst, 3.4 parts by weight of epoxysilane,
Otherwise, in the same manner as in the above-mentioned Example 2, a laminated material according to the present invention was manufactured in the same manner as in Example 2. 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 the filled and packaged product was manufactured, it had a high barrier property, no deterioration of the barrier property was observed, and it was also excellent in the fragrance retention of the contents, and further, excellent in the laminate strength. Results 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 composed of a solution of ethyl acetate and toluene 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, a linear low-density polyethylene and an ethylene-α-olefin copolymer polymerized using a metallocene catalyst were used on the surface of the anchor coating agent layer, and these were coextruded to a thickness of 30 μm. hand,
Heat-shear made of co-extruded film of 60 μm thickness
Then, a laminated material having the following layer constitution was manufactured by forming a conductive resin layer. Biaxially stretched nylon 6 film / silicon oxide vapor deposited film / anchor coating agent layer / heat-sealing resin layer Using the laminated material produced above, a three-way sealer with a Dunroll filling and packaging machine. 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.

Comparative Example 2 Thickness of 20 Formed 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-component curable polyurethane resin as in Example 2 above was applied to 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 film thickness of 1 μm to form an anchor coat agent layer, and then, on the anchor coat 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 sealable resin layer was formed to produce a laminated material having the following layer structure. Biaxially stretched nylon 6 film / deposited film of aluminum oxide / anchor coating agent layer / heat-sealing resin layer Using the laminated material produced above, a three-way sealer with a Dunroll filling and packaging machine. 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.

EXPERIMENTAL EXAMPLE 1 Each of the laminated materials produced in the above Examples 1 to 8 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 8, the surface of the coating thin film and the heat-sealing resin layer having a thickness of 60 μm were used. Surface, Comparative Example 1
Nos. 2 and 3 are heat-sealed with a surface of the deposited film and a thickness of 60 μm.
A laminate strength test and a tear test were performed on the surface of the resin layer. The laminating strength test was performed using a peel tester (Model name, Tensilon universal tester, manufactured by Orientec Co., Ltd.), a sample having a width of 15 mm and a peel angle of 90 mm.
Deposition was performed under the conditions of a load cell of 5 kgf and a peeling speed of 50 mm / min. In the tear test, a 5 mm cut was made at the end of the laminated material, the material was torn by hand, and the tear feeling was evaluated. The results are shown in Table 1 below.

[0051] In Table 1 above, the viewpoint of the tearing property means that ○ means tearing without resistance, and × means that the base material and the heat-sealing resin layer tear apart and do not tear.

As shown in the above Table 1, the laminates of Examples 1 to 8 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 Examples 1 to 8 and the laminated materials produced in Comparative Examples 1 and 2 were used, and the laminated materials were produced by bag making or box making. The following data was measured for the packaging container. (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.

[0054] 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 clear from the results shown in Table 2 above, those of Examples 1 to 8 were excellent in oxygen permeability and water vapor permeability, while those of Comparative Examples 1 to 8 were excellent.
Both of the two were inferior.

EXPERIMENTAL EXAMPLE 3 The laminated material manufactured in Examples 1 to 8 and the laminated material manufactured in Comparative Examples 1 and 2 were used, and were made into a bag or a box. And then put 1 dressing (blue diso dressing) in the pouch packaging container.
0 cc is filled and sealed to produce 250 sachets, then the sachets are placed in a pouch made of aluminum foil laminated packaging material and sealed at 37 ° C.
After storing for 2 days, the pouch was opened, and a sensory evaluation experiment was performed by five panelists. The results are shown in Table 3 below.

[0057] In Table 3 above, the organoleptic evaluation points were almost odorless.
Points, slightly odor 3 points, considerable odor 1 point, and the total score was evaluated. The highest score was 25 points.

As apparent from Table 3 above, Example 1
Samples Nos. To 8 had excellent preservability and excellent preservative properties, whereas those of Comparative Examples 1 and 2 were poor in preservative properties and lacked preservative properties.

[0059]

As is apparent from the above description, the present invention provides a barrier nylon film having gas barrier properties against oxygen gas, water vapor, etc., and excellent toughness such as impact resistance and piercing resistance. Focusing on the combination of an oxide thin film and a barrier resin layer made of a polyvinyl alcohol-based resin, a silane coupling agent having organic and inorganic properties, a polyurethane-based resin having an extensibility, a polyester-based resin, etc. A barrier resin layer of a resin composition containing a polyvinyl alcohol-based resin as a main component of a vehicle on one surface of a conductive nylon film, and one or two layers of inorganic oxide thin films on the other surface. The above-mentioned multilayer film is provided, and a primer composition containing a silane coupling agent or a polyester resin is further formed on the inorganic oxide thin film. A coating thin film made of an immersion composition is provided, and a laminating adhesive is formed on the surface of the coating thin film by a curing reaction between a polyester polyol or a polyether polyol and an isocyanate. A laminated material is manufactured by laminating at least a heat-sealing resin layer via the agent layer, and a bag for packaging is manufactured by making a bag or a box using the laminated material. And then
The content in the packaging container, particularly, filling and packaging a liquid or viscous content such as a liquid seasoning, and excellent transparency,
It has high barrier properties against oxygen gas or water vapor, etc., and also has excellent impact resistance, puncture resistance, laminating strength, etc., and has suitability for filling and packaging liquid or viscous contents and post-processing Occasionally there is no occurrence of cracks, etc., it has extremely high post-processing suitability, and even if it is subjected to microwave oven, it has sufficient microwave oven suitability, and various articles as packaging materials, especially liquid or viscous materials It is possible to produce a transparent barrier film having the suitability for packing the contents in a shape, a laminated material and a packaging container using the same, and the like.

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

FIG. 4 is a schematic perspective view showing the configuration of a packaging container made from a bag or a box using the laminated material according to the present invention.

FIG. 5 is a schematic configuration diagram illustrating an example of a roll-up type vapor deposition machine.

FIG. 6 is a schematic configuration diagram illustrating an example of a plasma chemical vapor deposition apparatus.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Barrier nylon film 2 Barrier resin layer 3 Inorganic oxide thin film 4 Coating thin film 5 Heat seal resin layer 6 Anchor coat agent layer 6a Laminate adhesive layer 7 Seal Part A Laminated material B Laminated material C Three-way seal type flexible packaging container D Two-side seal type flexible packaging container

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B65D 65/40 B65D 65/40 D 4J038 81/34 81/34 U 4J040 C08J 5/18 CEX C08J 5/18 CEX 4K029 CFG CFG 4K030 C08L 29/04 C08L 29/04 D 77/00 77/00 C09D 129/04 C09D 129/04 Z 175/04 175/04 C09J 129/04 C09J 129/04 Z 175/04 175/04 C23C 14/08 C23C 14/08 A 16/40 16/40 (72) Inventor Mitsunori Tsuzuki 1-1-1 Ichigaya-Kagacho, Shinjuku-ku, Tokyo Inside Dai Nippon Printing Co., Ltd. (72) Inventor Hideaki Takahashi Tokyo 1-1-1, Ichigaya-Kagacho, Shinjuku-ku Dainippon Printing Co., Ltd. (72) Inventor Hiroshi Yamamoto 1-1-1, Ichigaya-Kagacho, Shinjuku-ku, Tokyo In-house F term (reference) 3E086 AD01 AD02 BA04 BA15 BA24 BA40 BB01 BB15 BB22 BB31 BB51 BB62 CA01 CA11 CA35 4F071 AA15X AA29 AA29X AC05 AC16 AE02 AF07 AF19 AF23 AH05 BA03 BB02 BC01 BC02 4F100 AA01A06 A02A02A02A02B AK41D AK41G AK46A AK47A AK51D AK51G AK69A AK69B AL05B AL05D BA05 BA07 BA10B BA10E BA13 CA02B CA23D CB00 EC18 EH46 EH66C EJ08 EJ38A EJ65D EJ67D GB16 GB17 JD02A JD02B JD03 JD16 JK01 JK08 JK10 JL01 JL12E JM02C JN01 YY00 4F210 AA04 AA19 AA29 AD02 AD05 AD20 AD34 AG03 AG07 QC05 QD08 QG01 QG15 QG18 4J002 BB221 BE021 BE031 DD018 DF038 DG058 EC076 EF038 EN048 EX037 FD146 FD147 FD158 GF00 GG01 4J038 AA012 CE021 CE031 DM022 HA212 JA23 JC32 PA07 PB03 PB04 JA08 EA01A04J08 EA0131 BA43 BA44 CA07 CA12 DA08 LA01

Claims (18)

[Claims] 1. A barrier resin layer made of a resin composition containing a polyvinyl alcohol-based resin as a main component of a vehicle is provided on one surface of a barrier nylon film, and a thin film of inorganic oxide is provided on the other surface. And a coating thin film of a primer composition containing a silane coupling agent or a primer composition containing a polyester resin on the inorganic oxide thin film. And a laminated material having at least a heat-sealing resin layer laminated on the coating thin film. 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 polyvinyl alcohol-based resin is a polyvinyl alcohol resin or an ethylene-vinyl alcohol copolymer. 5. The laminate according to claim 1, wherein the resin composition contains a metal alkoxide compound and / or a hydrolyzate thereof. 6. The laminate according to claim 1, wherein the resin composition contains a crosslinking agent. 7. The laminate according to claim 1, wherein the resin composition contains a silane coupling agent. 8. The laminated material according to claim 1, wherein the inorganic oxide thin film comprises one or two or more inorganic oxide vapor-deposited films. 9. The laminate according to claim 1, wherein the inorganic oxide thin film comprises one or two or more inorganic oxide vapor-deposited films formed by physical vapor deposition. . 10. 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. . 11. The method according to claim 1, wherein the inorganic oxide thin film is composed of two or more layers of an inorganic oxide vapor-deposited film formed by physical vapor deposition and chemical vapor deposition. Laminated material. 12. 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. 13. The laminate according to claim 1, wherein the primer composition comprises a polyurethane resin composition containing a silane coupling agent and a filler. 14. The laminate according to claim 1, wherein the primer composition comprises a water / alcohol-based composition containing a silane coupling agent. 15. An anchor coating agent layer or a laminating layer between a coating thin film and a heat-sealing resin layer.
The laminated material according to any one of claims 1 to 14, wherein the laminated material is formed by laminating through an adhesive layer for the adhesive. 16. The laminating adhesive layer comprises a laminating adhesive layer formed by a curing reaction between a polyester polyol or polyetherpolyol and a polyfunctional isocyanate. A laminate according to claim 15 characterized by the above-mentioned. 17. The laminate according to claim 1, wherein the adhesive layer for laminating is JIS K.
23 ° C, 50% RH with No. 4 dumbbell according to 6301
300 mm / min. The laminated material according to claim 16, having a tensile elongation of 300% to 550% as measured under the following conditions: 18. A barrier resin layer of a resin composition containing a polyvinyl alcohol-based resin as a main component of a vehicle is provided on one surface of the barrier nylon film, and a thin film of inorganic oxide is provided on the other surface. A multilayer film of one or more layers is further provided, and a coating thin film of a primer composition or a polyester resin composition containing a silane coupling agent is provided on the inorganic oxide thin film; ,
A packaging container characterized by using a laminated material obtained by laminating at least a heat-sealing resin layer on the coating thin film, and forming the laminated material into a bag or a box.