JP2000238174A - 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 gas barrier properties against oxygen gas or steam, rich in aroma retentivity, impact resistance, thrust resistance and the preservability of content, having post-formability, excellent in lamination strength and good in the filling and packaging aptitude of content, especially, a liquid seasoning and a packaging container using the same. SOLUTION: A laminated material is obtained by providing a barrier resin layer 2 comprising a resin compsn. wherein a polyvinyl alcohol resin is a main component of a vehicle on one surface of a nylon film 1 and providing an inorg. oxide thin films or a multilayered film comprising two or more inorg. oxide thin films 3 on the other surface thereof and further providing a coating thin film 4 comprising a primer compsn. containing a silane coupling agent or a polyester resin compsn. on the inorg. oxide thin film 3 and furthermore providing at least one heat-sealable resin layer 5 on the coating thin film 4. This laminated material 5 is used to produce a packaging container.

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 containing a metal alkoxide or a hydrolyzate thereof as a main material has been proposed, but a substrate film using a nylon film or the like has been proposed.
In fact, it is impossible to solve the problem that the fragrance retention and the like are inferior to those using a polyethylene terephthalate film or the like. Therefore, the present invention
In view of the above circumstances, it has excellent transparency and high barrier properties against oxygen gas, water vapor, etc.
Rich in impact resistance, piercing resistance, preservability to contents, etc., and has good post-processing suitability, excellent laminating strength, and good filling and packaging suitability for contents, especially liquid seasonings. It is an object of the present invention to provide a laminated material and a packaging container using the same.

[0004]

The present inventors have conducted various studies to solve the above-mentioned problems, and as a result, have found that a biaxially stretched nylon film which is excellent in impact resistance, piercing resistance and the like, and which is rich in toughness, Focusing on a combination of a thin film of an inorganic oxide and a barrier resin layer 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, and the like, On one surface of the biaxially stretched 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 on the other surface, one layer of an inorganic oxide thin film or A multilayer film having two or more layers is provided, and a coating with a primer composition or a polyester-based resin composition containing a silane coupling agent is further formed on the inorganic oxide thin film. A film is provided, and at least a heat-sealing resin layer is laminated on the coating thin film to form a laminated material. The packaging container was manufactured by box making, and then the contents were packed and packed in the packaging container with liquid or viscous contents such as a liquid seasoning.
It has high barrier properties against oxygen gas or water vapor, etc. Furthermore, it has fragrance retention, impact resistance, piercing resistance, and laminating properties.
Excellent in strength, etc., and also excellent in preservability for liquid or viscous contents such as liquid seasonings, and without generation of cracks and the like in post-processing, having extremely high post-processing suitability,
Furthermore, even if the packaged product is microwaved, it is possible to produce a laminated material having sufficient microwave oven aptitude and filling aptitude for various articles as a packaging material, and a packaging container and the like using the same. And completed the present invention.

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 nylon film.
On the other side, a multilayer film of one or more layers of an inorganic oxide thin film is provided, and further, on the inorganic oxide thin film,
A coating thin film made of a primer composition or a polyester-based resin composition containing a silane coupling agent is provided, and at least a heat-sealing resin layer is laminated on the coating thin film. And a packaging container using the same.

[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 nylon film 1, a barrier resin comprising a resin composition containing a polyvinyl alcohol-based resin as a main component of a vehicle. Layer 2 is provided, and on the other side,
One or two or more multilayer films (not shown) of the inorganic oxide thin film 3 are provided, and a primer composition containing a silane coupling agent on the inorganic oxide thin film 3 or Coating thin film 4 made of polyester resin composition
Further, the basic structure is such that at least a heat-sealing resin layer 5 is laminated on the coating 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 a laminated material B formed by laminating at least a heat-sealing resin layer 5 via an anchor coating agent layer 6 or a laminating adhesive layer 6a. Can be. 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, etc., depending on the purpose of use, the contents to be filled and packaged, the distribution channel, the sales form, the application, etc.
It is possible to design and manufacture various types of laminated materials by arbitrarily laminating other base materials. In the present invention, a thin film of an inorganic oxide, a coating thin film of a primer composition or a polyester resin composition containing a silane coupling agent, an anchor coating agent layer, or a laminating agent It is important for the adhesive layer to be laminated adjacent to each other in this order in order to exhibit a function and effect such as close adhesiveness, but the other base materials are used for their purposes, applications, etc. Thus, various types of laminated materials can be designed and manufactured by arbitrarily laminating. Further, in the present invention, the nylon film 1 is provided with 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 and 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 providing an inorganic oxide thin film 3, a coating thin film 4, a barrier resin layer 2, and a heat-sealing resin layer 5 on the nylon film 1 in this order. It can be manufactured through any process such as a process 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 laminated material A shown in FIG. The surfaces of the heat-sealable resin layers 5 and 5 are overlapped with 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-mentioned two-way seal type flexible packaging container D, the contents are filled from the opening above it, 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 nylon film constituting the laminated material, the packaging container, etc. according to the present invention is excellent in impact resistance, puncture resistance, etc., rich in toughness, and further holds a thin film of inorganic oxide. Polyamide resin film or sheet
Any material can be used. Specifically, for example, various polyamide resin (nylon) films or sheets such as nylon 46, nylon 6, nylon 66, nylon 610, nylon 612, nylon 7, nylon 11, nylon 12, and the like are used. can do. The polyamide-based resin (nylon) film or sheet can be formed by a conventional one such as a tenter method or a tuber method.
It is desirable to use a film or sheet of a biaxially stretched polyamide resin (nylon) which has been stretched in a biaxial direction by a biaxial stretching method, and has a thickness of 5 to 200 μm. Position, preferably 10 to 100 μm
Position is desirable. The polyamide resin film or sheet may be subjected to a surface smoothing treatment by coating an anchor coating agent or the like, if necessary.
Further, a surface treatment such as a corona discharge treatment, a plasma discharge treatment, an ozone treatment, a flame treatment, and the like can be arbitrarily performed. In the present invention, by using the above-mentioned polyamide resin (nylon) film or sheet as a base material, the toughness such as the strength, impact resistance and piercing resistance of the film or sheet is utilized. Thus, a laminated material having these characteristics can be manufactured.

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, an 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
Etc. can be used. Further, in the present invention,
As the polyfunctional compound described above, for example, -CH = CH
_TwoGroup, = C = O group, -C≡N group, epoxy group, ethylene
Compounds having functional groups that react with active hydrogen such as imine groups
, -OH group, -SH group, -COOH group, -NH_TwoBase
A compound having active hydrogen, other, a halogen group, a salt,
Use a cross-linking agent consisting of a compound having a chelate forming group, etc.
Can be used. Specifically, for example,
Compounds, dicarboxylic acid compounds, diimide compounds,
Chair polyhydric alcohol compounds, diamine compounds, diisocyanates
Anat compounds, bisepoxy compounds, bisethylene compounds
Min compounds, divinyl compounds, zirconium compounds,
Tankile compounds and others can be used.
You.

Next, in the present invention, a silane coupling agent having 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, a 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 method is excellent in tight adhesion to the nylon film, the bonding strength between the two is extremely strong, and no phenomenon such as peeling between the layers is observed. The thin film of the product and the above-mentioned barrier resin layer are synergistically constituted to constitute a barrier film, whereby the barrier property against oxygen gas, water vapor gas, etc. is remarkably improved, and the transparency and heat resistance are improved. It is also excellent in 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 laminated material, 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 amorphous thin film 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, the inorganic oxide thin film includes one of the above-described inorganic oxide thin films,
Alternatively, an inorganic oxide thin film composed of a multilayer film of two or more inorganic oxide thin films is used. In the present invention, a method for forming one or two or more layers of inorganic oxide thin films on a nylon film will be described. Vapor Depth Method (Physical Vapor Depth Method)
chemical vapor deposition (PVD), or a chemical vapor deposition method such as a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, or a photochemical vapor deposition method.
(e.g., deposition method, CVD method). In the present invention, to further explain the film-forming method, for example, using a metal oxide as a raw material, a vacuum evaporation method of heating and vaporizing and vapor-depositing on a nylon film, or Oxidation reaction deposition method of using metal or metal oxide as the raw material, introducing oxygen to oxidize and depositing on a nylon film, and plasma-assisted oxidation reaction deposition method of assisting the oxidation reaction with plasma, etc. Can be used to form a deposited film. 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 metal or metal oxide to be used and the like.
It is desirable to arbitrarily select and form in the range of about 2000 °, preferably about 100 to 1000 °,
As the thickness of a multilayer film of two or more inorganic oxide thin films,
100 ~ 4000４, preferably 120 ~ 2000
The Å position is desirable.

In the present invention, a specific example of a method for forming a multilayer film of one or two or more inorganic oxide thin films is shown in FIG. 5. FIG. It is a schematic block diagram. As shown in FIG. 5, a nylon film 113 unwound from an unwinding roll 112 in a vacuum chamber 111 is coated with a coating drum 1.
14 and into the evaporation chamber-115, where the evaporation source heated by the crucible 116 is evaporated, and if necessary, the above-described cooling is performed while oxygen or the like is ejected from the oxygen outlet 117. Coating drum 11
4 on a nylon film 113, a mask 118,
A vapor-deposited inorganic oxide film is formed via a film 118, and then the nylon film 113 on which the vapor-deposited film is formed is fed into a vacuum chamber 111.
The nylon film 113 having an inorganic oxide thin film can be manufactured by winding the film 9. 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 forming method in which two or more inorganic oxide thin films are laminated by the above-described plasma chemical vapor deposition method will be described. FIG.
1 is a schematic configuration diagram illustrating an example of a plasma chemical vapor deposition apparatus. As shown in FIG.
The nylon film 214 is unwound from the unwinding roll 213 disposed in the vacuum chamber -212 of
It is conveyed at a constant speed via the auxiliary roll 215, and is then supplied on the peripheral surface of the cooling / electrode drum 216 from the raw material volatile supply devices 217, 218, 219, for example, an organic silicon compound, oxygen gas, A mixed gas comprising an inert gas or the like is introduced through the raw material supply nozzle 220, and the nylon film 21 is supplied by the glow discharge plasma 221.
4, a thin film of an inorganic oxide such as a vapor-deposited film of silicon oxide is formed and formed into a film.
Is a power supply 22 arranged outside the vacuum chamber-212.
2, and a magnet 223 is disposed near the cooling / electrode drum 216 to promote the generation of plasma. Nylon film 2 with a thin film of material
Reference numeral 14 denotes a take-up roll 22 via an auxiliary roll 215.
4, and a nylon film having a thin film of an inorganic oxide can be produced. 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 drawing, reference numeral 225 denotes 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 made of a primer composition containing a silane coupling agent constituting 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 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, polymethylene polyphenylene polyisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, etc. 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 of the polyester resin composition constituting the laminate according to the present invention will be described. As the polyester resin, for example, a benzene nucleus such as terephthalic acid is used. A thermoplastic polyester resin formed by polycondensation of one or more aromatic saturated dicarboxylic acids having a basic skeleton and one or more saturated divalent alcohols can be used. In the above description, as the aromatic saturated dicarboxylic acid having a benzene nucleus as a basic skeleton, for example, terephthalic acid, isophthalic acid, phthalic acid, diphenyl ether-4, 4-dicarboxylic acid, and the like can be used. In the above, the saturated divalent alcohol includes ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, diethylene glycol, polyethylene glycol.
, Polypropylene glycol, polytetramethylene glycol, hexamethylene glycol, dodecamethylene glycol, aliphatic glycols such as neopentyl glycol, and alicyclic glycols such as cyclohexanedimethanol. −
, 2.2-bis (4'-β-hydroxyethoxyphenyl) propane, naphthalenediol, other aromatic di-, and the like can be used. 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, and a copolymer 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, terephthalic acid, ethylene glycol and 1,4-cyclohexanedimethanol
A thermoplastic polyethylene terephthalate resin formed by copolycondensation with styrene, a thermoplastic polyethylene terephthalate resin formed by copolycondensation of terephthalic acid, isophthalic acid, ethylene glycol and propylene glycol, Polyester polyol resins and others can be used. In the present invention, the above-mentioned saturated aromatic dicarboxylic acid having a benzene nucleus as a basic skeleton further includes, for example, malonic acid, succinic acid, glutaric acid,
Adipic acid, pimelic acid, suberic acid, azelaic acid,
Sebacic acid, one or more of aliphatic saturated dicarboxylic acids such as dodecanoic acid can be added for copolycondensation, and the amount thereof is based on the amount of aromatic saturated dicarboxylic acid having a benzene nucleus as a basic skeleton. It is preferable to add about 1 to 10% by weight for use.

Thus, in the present invention, the polyester resin composition comprises one or more of the above polyester resins as a main component of a vehicle,
If necessary, for example, silane coupling agent, filler,
One or more additives such as a stabilizer, a curing agent, a cross-linking agent, a lubricant, an ultraviolet absorber, etc. are arbitrarily added, and a solvent, a diluent, etc. are added and kneaded sufficiently to obtain a polyester resin composition. To adjust. Thus, in the present invention, the above-mentioned polyester-based resin composition can be used, for example, by roll coating, gravure coating, knife coating, dip coating.
According to the present invention, coating is performed on an inorganic oxide thin film by a coating method such as spray coating or other coating method, and then the coating film is dried to remove a solvent, a diluent and the like. A coating thin film can be formed. In the present invention, the thickness of the coating thin film of the polyester-based resin composition is, for example, 0.01 to
About 50 μm, preferably about 0.1 to 5 μm is desirable.

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. Specific examples include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, and 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 copolymers, methylpentene polymers, polybutene polymers, polyolefin resins 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 in which the layers are laminated via an agent layer, or an extrusion lamination method in which the layers are laminated through a melt-extruded resin layer made 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, a 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 a barrier property 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, sealing property, quality maintenance, workability, hygiene, etc. are required. A material that satisfies the above conditions can be arbitrarily 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-described 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 may be used for various articles such as various foods and drinks, chemicals such as adhesives and pressure-sensitive adhesives, cosmetics, pharmaceuticals, and the like.
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.

[0039]

EXAMPLES The present invention will be described more specifically with reference to examples. Example 1 First, on one surface of a biaxially stretched nylon 6 film having a thickness of 15 μm, a film having a thickness of 2 μm was formed by chemical vapor deposition (CVD).
A deposited film of silicon oxide of 00 ° was formed. Next, as a silane coupling agent, N-β (aminoethyl) -γ-
Using aminopropyltrimethoxysilane, 1.0% by weight of the silane coupling agent, 1.0% by weight of silica powder, 13 to 15% by weight of polyurethane resin, 3 to 4% by weight of nitrocellulose, 31 to 38% of toluene A polyurethane-based resin composition was prepared which consisted of 30% by weight, 29-30% by weight of methyl ethyl ketone (MEK), and 15-16% by weight of isopropyl alcohol (IPA). Next, using the above-mentioned polyurethane-based resin composition, this was applied to the surface of the above-formed silicon oxide film having a thickness of 200 ° by gravure coating.
Using a coating method, coating is performed, and then 100
The coating was dried at a temperature of 5 ° C. for 5 seconds to form a coating thin film (0.4 g / m ^{2 in} a dry state) made of the above polyurethane resin composition. 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. Using an adhesive for laminating, this is coated to a film thickness of 1 μm by a gravure roll coating method to form an adhesive layer for laminating, and then the laminating adhesive is formed.
On the surface of the adhesive layer, a linear low-density polyethylene and an ethylene-α-olefin polymerized using a metallocene catalyst are used, and these are coextruded to a thickness of 30 μm and coextruded to a thickness of 60 μm. A heat-sealing resin layer made of a film was formed. Next, the thickness of 15 μm
On the other side of the biaxially stretched nylon 6 film, ion-exchanged water of an 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
A barrier resin layer was formed by performing a heat treatment at 120 ° C. for 5 minutes to produce a laminated material according to the present invention having the following layer configuration. Barrier resin layer /
Biaxially stretched nylon 6 film / silicon oxide deposited film /
Thinning film / Laminate adhesive layer / Heat-sealing resin layer Next, using the laminated material produced above,
A three-sided seal-type plastic bag was produced by a filling and packaging machine, and a liquid seasoning was filled. Thereafter, the opening was heat-sealed to produce a filled and packaged product.
It had a high barrier property, no deterioration of the barrier property was recognized, and very good results with excellent laminating strength were obtained.

Example 2 First, a vapor-deposited aluminum oxide film having a thickness of 200 ° was formed on one surface of a biaxially stretched nylon 6 film having a thickness of 15 μm by physical vapor deposition (PVD). On the other hand, a polyester resin composition containing a thermoplastic polyethylene terephthalate resin as a main component of the vehicle was prepared (solid content: 10%). Next, using the above-mentioned polyester-based resin composition, a 200 ° -thick aluminum oxide vapor-deposited film is coated by a gravure roll coating method, and then coated at 100 ° C. And dried for 5 seconds to form a coating thin film (thickness 0.3 g / m ² , dry state) of the polyester resin composition. A polyether film is formed on the surface of the coating thin film formed above.
A two-part curable polyurethane resin composed of terpoliol and isocyanate is used as a laminating adhesive composed of a 7% solution of ethyl acetate and toluene in a toluene solution. To form a laminating adhesive layer by coating to a thickness of 1 μm, and then a linear low-density polyethylene and ethylene polymerized using a metallocene catalyst are formed on the laminating adhesive layer. -Α-olefin was used and coextruded to a thickness of 30 μm to form a heat-sealing resin layer composed of a coextruded film having a thickness of 60 μm. Next, the thickness 15
On the other side of the biaxially stretched nylon 6 film of μm, an ethylene-vinyl alcohol copolymer (ethylene content 32
Aqueous resin consisting of 10 parts by weight, 34 parts by weight of tetraethoxysilane, 15 parts by weight of water, 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 Use the composition,
This was coated by a gravure roll coating method to form a coating film having a thickness of 0.9 g / m ² (dry state), and then heat-treated at 120 ° C. for 1 minute to form a barrier resin. Layers were formed to produce a laminate according to the present invention having the following layer configuration. Barrier resin layer / biaxially stretched nylon 6
Film / aluminum oxide deposited film / coating thin film / laminate adhesive layer / heat-sealing resin layer Next, using the laminated material produced above, a three-way sealing machine is used by a die roll filling and packaging machine. -To manufacture a plastic bag in the form of a roll and fill it with a liquid seasoning.
When the filled packaged product was manufactured by tosealing, it had a high barrier property, no deterioration of the barrier property was recognized, and very good results with excellent laminate strength were obtained.

Example 3 First, a biaxially-stretched nylon 6 film having a thickness of 15 μm was provided with two layers of a 150-mm-thick silicon oxide vapor-deposited film by chemical vapor deposition (CVD) on one surface. To form a multilayer film. On the other hand, as a silane coupling agent,
Using N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, 1.0% by weight of the silane coupling agent was added to water: isopropyl alcohol (IPA) =
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 1: 1 mixed solvent. Next, using the water / alcohol-based composition prepared above, the thickness of 15
Two layers of 0 ° silicon oxide deposition film are layered, and the silicon oxide deposition film surface as a multilayer film is coated using a gravure roll coating method, and then dried at 120 ° C. for 20 seconds. Then, a coating thin film (thickness 0.5 g / m ² , dry state) was formed from the above-mentioned water / alcohol-based composition.
Next, on the surface of the coating thin film formed as described above, a two-part curable polyurethane resin composed of polyetherpolyol and isocyanate was bonded to a laminate composed of a 7% ethyl acetate and toluene solution of 7%. Using a gravure roll coating method, this was coated to a film thickness of 1 μm to form an adhesive layer for laminating. Then, on the adhesive layer surface for laminating, A linear low-density polyethylene and an ethylene-α-olefin polymerized using a metallocene catalyst are used, each of which is coextruded 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, the thickness 15
On one side of a biaxially stretched nylon 6 film of μm, an ethylene-vinyl alcohol copolymer (ethylene content 32
Aqueous resin consisting of 10 parts by weight, 34 parts by weight of tetraethoxysilane, 15 parts by weight of water, 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 Use the composition,
This was coated by a gravure roll coating method to form a coating film having a thickness of 0.9 g / m ² (dry state), and then heat-treated at 120 ° C. for 1 minute to form a barrier resin. Layers were formed to produce a laminate according to the present invention having the following layer configuration. Barrier resin layer / biaxially stretched nylon 6
2 layers of film / silicon oxide vapor deposition / coating thin film /
Adhesive Layer for Laminate / Heat Sealing Resin Layer Next, 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 prepared. And then the opening is heat-sealed.
As a result, the product had high barrier properties, no deterioration of the barrier properties was observed, and excellent results with excellent laminate strength were obtained.

Example 4 First, a biaxially stretched nylon 6 film having a thickness of 15 μm was coated on one surface with a thickness of 2 μm by physical vapor deposition (PVD).
Two layers of deposited aluminum oxide films of 00 ° were laminated 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 (solid content: 15%). Next, using the above-mentioned polyester-based resin composition, two layers of the deposited aluminum oxide film having a thickness of 200 ° formed as described above are layered in two layers. Coating using a gravure roll coating method, followed by drying at 100 ° C. for 5 seconds to obtain a coating thin film (thickness: 0.1 mm) of the above polyester resin composition.
3 g / m ² , dry). Next, on the surface of the coating thin film formed as described above, a laminating adhesive comprising a 7% ethyl acetate and toluene solution of a two-component curable polyurethane resin composed of polyester polyol and isocyanate. This is coated by a gravure roll coating method to a film thickness of 1 μm to form an adhesive layer for laminating, and then a line is formed on the surface of the adhesive layer for laminating. Using low-density polyethylene and ethylene-α-olefin polymerized using a metallocene catalyst,
Each of them is co-extruded to a thickness of 30 μm and has a thickness of 60 μm.
A heat-sealing resin layer made of a co-extruded film having a thickness of μm was formed. Next, on the other surface of the biaxially stretched 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 obtained by adding 1 part by weight of a 30% solution of zirconium acetate in the same solvent to 100 parts by weight of a 15% solution in a solvent is used, and this is coated by a gravure roll coating method.
To a 1.1 g / m ² (dry state) core
A barrier resin layer was formed by performing a heat treatment at 120 ° C. for 5 minutes to produce a laminated material according to the present invention having the following layer configuration. Barrier resin layer /
Biaxially stretched nylon 6 film / aluminum oxide vapor deposition film 2 layers / coating thin film / laminate adhesive layer / heat-sealing resin layer A three-sided seal-type plastic bag was produced by a filling and packaging machine, and a liquid seasoning was filled. Thereafter, the opening was heat-sealed to produce a filled and packaged product. And no deterioration of the barrier properties was observed, and very good results with excellent laminating strength were obtained.

Example 5 One side of a biaxially stretched nylon 6 film having a thickness of 15 μm was formed on a surface of 200 mm thick by chemical vapor deposition (CVD).
A silicon oxide vapor deposition film is formed on the silicon oxide vapor deposition film, and a thickness of 2 nm is formed on the silicon oxide vapor deposition film by physical vapor deposition (PVD).
A deposited film of aluminum oxide with a thickness of 00 ° was formed, and a two-layer deposited film was overlaid to form a multilayer film. Next, a polyester resin composition containing thermoplastic polyethylene terephthalate resin as a main component of the vehicle was prepared (solid content: 15%).
%). 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 above-described two-layer vapor-deposited film. And coat, then 1
The coating was dried at 00 ° C. for 5 seconds to form a coated thin film (thickness: 0.3 g / m ² , dry state) of the above polyester resin composition. 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 as described above. Using an adhesive for laminating, this is coated to a film thickness of 1 μm by a gravure roll coating method to form an adhesive layer for laminating. A linear low-density polyethylene and an ethylene-α-olefin copolymer polymerized using a metallocene catalyst are used on the surface of the adhesive layer, and these are coextruded to a thickness of 30 μm to form a 60 μm A heat-sealing resin layer made of an extruded film was formed. Next, on the other surface of the biaxially stretched 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) 100% by weight of a 15% solution in a solvent and 1% of a 30% solution of carbodiimide in the same solvent.
A resin composition to which a part by weight was added was used, and this was coated by a gravure roll coating method to obtain a resin composition having a thickness of 1.1 g /
forming a coating film of m ² (dry state);
Heat treatment was performed at 120 ° C. for 5 minutes to form a barrier resin layer, and a laminated material according to the present invention having the following layer constitution was manufactured. Barrier resin layer / biaxially stretched nylon 6 film / silicon oxide deposited film / aluminum oxide deposited film / coating thin film / laminate adhesive layer / heat seal resin layer Using a material, a three-sided seal-type plastic bag is produced by a die-roll filling and packaging machine, and at the same time, a liquid seasoning is filled. Thereafter, the opening is heat-sealed to produce a filled packaging product. As a result, it had a high barrier property, no deterioration of the barrier property was recognized, and very good results with excellent laminate strength were obtained.

Example 6 First, a biaxially stretched nylon 6 film having a thickness of 15 μm was coated on one surface with a thickness of 2 μm by physical vapor deposition (PVD).
Then, a deposited film of aluminum oxide was formed on the deposited aluminum oxide film, and then a chemical vapor deposition method (C
VD) was used to form a 200-mm-thick silicon oxide vapor-deposited film, and a two-layer vapor-deposited film was stacked to form a multilayer 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, polyurethane resin was 13 to 15% by weight, Nitrocellulose 3 ~
A polyurethane resin composition comprising 4% by weight, 31 to 38% by weight of toluene, 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, 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 dried at 120 ° C. for 20 seconds to form a coating thin film (1.0 g in thickness) of the polyurethane resin composition.
/ M ² , dry state). On the coated thin film surface of the polyurethane resin composition formed as described above, a two-part curable polyurethane resin composed of polyetherpolyol and isocyanate, a laminate composed of a 7% ethyl acetate and toluene solution of 7%. Using the adhesive for
Using a gravure roll coating method, coat to a film thickness of 1 μm.
To form a laminating adhesive layer, and then
On the surface of the laminating adhesive layer, a linear low-density polyethylene and ethylene-α-polymerized using a metallocene catalyst were used.
Olefin copolymers, each having a thickness of 30
Co-extruded to a thickness of 60 μm to form a heat-sealing resin layer made of a co-extruded film having a thickness of 60 μm. next,
On the other surface of the biaxially stretched nylon 6 film having a thickness of 15 μm, 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, Isopropyl alcohol
An aqueous resin composition consisting of 10 parts by weight of a tertiary amine catalyst, 0.17 parts by weight of a tertiary amine catalyst, and 3.4 parts by weight of an epoxy silane was used. A coating film having a thickness of 0.9 g / m ² (dry state) was formed, and then heat-treated at 120 ° C. for 1 minute to form a barrier resin layer. The laminated material was manufactured. Barrier resin layer / biaxially stretched nylon 6 film / aluminum oxide deposited film / silicon oxide deposited film / coating thin film / laminate adhesive layer / heat-sealing resin layer Using a material, a three-sided seal type plastic bag is produced by a die roll filling and packaging machine, and a liquid seasoning is filled. Thereafter, the opening is heat-sealed to produce a filled packaging product. As a result, it had a high barrier property, no deterioration of the barrier property was recognized, and very good results with excellent laminate strength were obtained.

Example 7 In Example 1, 15% of ethylene-vinyl alcohol copolymer (ethylene content: 32 mol%) in ion-exchanged water and n-propyl alcohol (1/1) solvent was used.
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 manufactured as described above, a three-sided seal-type plastic bag is manufactured by a die roll filling and packing 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 recognized, and very good results with excellent laminate strength were obtained.

Example 8 In Example 2, 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 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 Parts by weight, a tertiary amine catalyst 0.17 parts by weight, using an aqueous resin composition consisting of 3.4 parts by weight of epoxy silane,
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 manufactured as described above, a three-sided seal-type plastic bag is manufactured by a die roll filling and packing 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 recognized, and very good results with excellent laminate strength were obtained.

COMPARATIVE EXAMPLE 1 A thickness of 20 formed by chemical vapor deposition (CVD)
A biaxially stretched nylon 6 film having a thickness of 15 μm and a silicon oxide film having a thickness of 200 μm having a vapor deposition film of silicon oxide having a thickness of 0 ° is coated with 7% of the same two-component curable polyurethane resin as in Example 1 above. A laminating adhesive layer consisting of ethyl acetate and a toluene solution was used, and this was coated to a film thickness of 1 μm by a gravure roll coating method to form a laminating adhesive layer. Next, a linear low-density polyethylene and an ethylene-α-olefin copolymer polymerized using a metallocene catalyst were used on the surface of the adhesive layer for laminating, and these were coextruded to a thickness of 30 μm. Of a co-extruded film having a thickness of 60 μm.
By forming a sealable resin layer, a laminated material having the following layer structure was manufactured. Biaxially stretched nylon 6 film / vapor-deposited film of silicon oxide / adhesive layer for laminating / heat-sealing resin layer Using the laminated material produced above, a three-way seal using 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.

Comparative Example 2 Thickness of 20 Formed Using Physical Vapor Deposition (PVD)
15 μm thick with a deposited film of 0 ° aluminum oxide
Adhesion for laminating consisting of a 7% ethyl acetate and toluene solution of the same two-part curable polyurethane resin as in Example 2 above, on the surface of the biaxially stretched nylon 6 film of aluminum oxide having a thickness of 200 mm. Using a gravure roll coating method, this was coated to a film thickness of 1 μm to form an adhesive layer for laminating. Then, on the adhesive layer surface for laminating, Linear low density polyethylene,
And an ethylene-α-olefin copolymer polymerized using a metallocene catalyst, each having a thickness of 30 μm.
To form a heat-sealing resin layer composed of a co-extruded film having a thickness of 60 μm, thereby producing a laminated material having the following layer constitution. Biaxially stretched nylon 6 film / aluminum oxide vapor deposited film / laminate adhesive layer / heat-sealing resin layer A plastic bag of a mold was produced and filled with a liquid seasoning, and then the opening was heat-sealed to produce a filled packaging product.

EXPERIMENTAL EXAMPLE 1 Each of the laminated materials produced in 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.

[0050] In Table 1 above, the viewpoint of the tearing property is that は means tearing without resistance, and × means tearing of the base material and the heat-sealing resin layer and not tearing. .

As shown in Table 1 above, the laminates of Examples 1 to 8 have significantly higher laminating strength than those of Comparative Examples 1 and 2, and thus a coating thin film is formed. 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.

[0053] 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 the resultant was formed 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.

[0056] 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.

[0058]

As apparent from the above description, the present invention provides a barrier film made of a tough nylon film, an inorganic oxide thin film and a polyvinyl alcohol-based resin having excellent impact resistance and piercing resistance. Focusing on a combination with a hydrophilic resin layer, a silane coupling agent having organic and inorganic properties, an extensible polyurethane-based resin, a polyester-based resin, and the like, a polyvinyl alcohol-based resin is provided on one surface of the nylon film. Is provided with a barrier resin layer of a resin composition containing a main component of a vehicle, and on the other side, a multilayer film of one or more inorganic oxide thin films is further provided.
On the inorganic oxide thin film, a coating thin film of a primer composition or a polyester-based resin composition containing a silane coupling agent is provided, and a polyester polyol or polyester is further formed on the coating thin film surface. A laminated material is manufactured by laminating at least a heat-sealing resin layer via a laminating adhesive layer formed by a curing reaction between terpoliol and isocyanate; Then, using the laminated material to make a bag or a box to produce a packaging container, and then filling the packaging container with contents, particularly liquid or viscous contents such as a liquid seasoning. Packed, has excellent transparency and high barrier properties against oxygen gas or water vapor, and has excellent impact resistance, puncture resistance, laminating strength, etc., and is filled with liquid or viscous contents. Suitable for packaging In addition, there is no occurrence of cracks and the like during post-processing, and it has extremely high post-processing suitability.Furthermore, even if the packaged product is subjected to microwave oven, it has sufficient microwave oven suitability, and various articles as packaging materials, especially In addition, it is possible to manufacture a transparent barrier film having suitability for packaging liquid or viscous contents, a laminated material and a packaging container using the same.

[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 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 code FI Theme coat ゛ (Reference) B32B 27/36 B32B 27/36 B65D 65/40 B65D 65/40 D 81/34 81/34 V C08J 7 / 04 CFG C08J 7/04 CFGB C23C 14/08 C23C 14/08 A 14/10 14/10 16/40 16/40 (72) Inventor Mitsunori Tsuzuki 1-1-1 Kagamachi, Ichigaya-cho, Shinjuku-ku, Tokyo, Japan Inside Printing Co., Ltd. (72) Inventor Hideaki Takahashi 1-1-1, Ichigaya-Kagacho, Shinjuku-ku, Tokyo Within Dai Nippon Printing Co., Ltd. F-term in Dai Nippon Printing Co., Ltd. (reference) AH06H AK21B AK41D AK48A AK51D AK69B AR00E BA05 BA07 BA11 CA02D CA30D CB00 EH66C EJ38A EJ65 EJ67 GB16 JD01B JD03 JD04 JJ03 JK08G JK10 JL00 JL01 JL12E JN01 AY44G04 A03A04A04A03

Claims (17)

[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 nylon film, and a thin film of inorganic oxide is provided on the other surface. Providing a layer or a multilayer film of two or more layers,
Further, a coating thin film made of a primer composition or a polyester resin composition containing a silane coupling agent is provided on the inorganic oxide thin film.
A laminated material comprising at least a heat-sealing resin layer laminated on a thinning film. 2. The laminated material according to claim 1, wherein the nylon film is a biaxially stretched nylon film. 3. The laminate according to claim 1, wherein the polyvinyl alcohol-based resin is a polyvinyl alcohol resin or an ethylene-vinyl alcohol copolymer. 4. The laminate according to claim 1, wherein the resin composition contains a metal alkoxide compound. 5. The laminate according to claim 1, wherein the resin composition contains a crosslinking agent. 6. The laminate according to claim 1, wherein the resin composition contains a silane coupling agent. 7. The laminated material according to claim 1, wherein the inorganic oxide thin film comprises one or two or more inorganic oxide vapor-deposited films. 8. 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. . 9. The laminate according to claim 1, wherein the inorganic oxide thin film is composed of one or more layers of an inorganic oxide vapor-deposited film formed by a chemical vapor deposition method. . 10. The method according to claim 1, wherein the inorganic oxide thin film is composed of two or more layers of a deposited inorganic oxide film formed by physical vapor deposition and chemical vapor deposition. Laminated material. 11. The laminate according to claim 1, wherein the deposited film of the inorganic oxide comprises a deposited film of silicon oxide or aluminum oxide. 12. The laminate according to claim 1, wherein the primer composition comprises a polyurethane resin composition containing a silane coupling agent and a filler. 13. The laminate according to claim 1, wherein the primer composition comprises a water / alcohol-based composition containing a silane coupling agent. 14. 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 13, wherein the laminated material is formed by laminating via an adhesive layer. 15. The laminating adhesive layer comprising a laminating adhesive layer formed by a curing reaction between a polyester polyol or a polyether polyol and a polyfunctional isocyanate. A laminate according to claim 14 characterized by the above-mentioned. 16. The adhesive layer for laminating is made of JIS K
23 ° C, 50% RH with No. 4 dumbbell according to 6301
300 mm / min. The laminate according to claim 15, wherein the laminate has a tensile elongation of 300% to 550% as measured under the following conditions. 17. 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 nylon film, and on the other surface,
One or more multilayer films of inorganic oxide thin films are provided, and a coating of a primer composition or a polyester resin composition containing a silane coupling agent is further formed on the inorganic oxide thin film. Providing a thin film, and
A packaging container characterized by using a laminated material in which at least a heat-sealing resin layer is laminated on a thinning film, and making this into a bag or a box.