JPH11286068A - Transparent barrier film, laminated material and packaging container using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an excellent transparency and high barrier properties or the like by providing a thin film of an inorganic oxide on one surface of a flexible plastic base material, and further providing a coating thin film made of water and alcohol based composition containing a silane coupling agent thereon. SOLUTION: The transparent barrier film 1 comprises a thin film 3 of an inorganic oxide provided on one surface of a flexible plastic base material 2, and a coating thin film 4 of a water and alcohol based composition containing a silane coupling agent. Then, a laminate material A obtained by laminating at least a heat sealable resin layer 6 on a surface of the film 4 via an adhesive layer 5. The two materials A are, for example, prepared. A surface of the layer 6 disposed on its innermost layer is opposed to the materials A, and superposed. Three sides of an end of an outer periphery are heat sealed to form a sealing portion. After a content is filled in the sealing portion, its opening is heat sealed to manufacture a packaging product.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent barrier film, a laminated material and a packaging container using the same, and more particularly, to excellent transparency, excellent barrier properties against water vapor or oxygen gas, impact resistance, and the like. Having good storage suitability, food packaging field, pharmaceutical packaging field, detergent, shampoo, oil, filling and packaging suitability of various articles in non-food fields such as toothpaste, and further, with microwave oven suitability, The present invention also relates to a transparent barrier film excellent in post-processing suitability, and a laminate and a packaging container using the same.

[0002]

2. Description of the Related Art Conventionally, various materials have been developed and proposed as packaging materials having a barrier property against oxygen gas and water vapor and having a good storage suitability. A transparent barrier film composed of a flexible plastic substrate on which a vapor-deposited film of an inorganic oxide such as silicon oxide or aluminum oxide is provided, a packaging laminate and a packaging container using the same are proposed. ing. This is superior in transparency to packaging laminates using conventional aluminum foil and the like, and has high barrier properties and aroma retention properties against water vapor, oxygen gas, and the like,
Further, 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 and the laminated material for packaging using the same is higher than that of the original barrier material, aluminum foil, for oxygen, water vapor and the like. Is inferior. For this reason, in the above-mentioned transparent barrier film, in a laminated material for packaging and the like using the same, to increase the barrier performance, the thickness of the deposited film is increased,
Alternatively, it is necessary to increase the thickness of the entire barrier layer.
However, in the above-described transparent barrier film, and a packaging laminate using the same, the barrier layer itself consisting of a deposited film of an inorganic oxide is inferior in flexibility, so that the film is rolled, or When it is bent, cracks are easily generated in the deposited film.For example, when post-processing such as printing or laminating, if the above operation is employed, cracks are easily generated, and once cracks are generated. In addition, there is a problem that the barrier property is 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. Furthermore, when a film or sheet of another resin is extruded onto the transparent barrier film as described above and subjected to a coating process or a dry laminating process, a transparent barrier film is produced. There is also a problem that the adhesive strength between the film and the laminating adhesive, the anchor coating agent, etc. is low, and further, the laminating strength is poor, and there is a problem that delamination often occurs. . Thus, in the above, a pretreatment such as a corona treatment may be performed in order to improve the adhesive strength with the adhesive, but the effect is not so much recognized in the transparent barrier film. There is a problem of scratching. In view of the above circumstances, the present invention has excellent transparency and high barrier properties, furthermore, is excellent in impact resistance, has post-processing suitability, and further has excellent laminating strength. It is an object of the present invention to provide a transparent barrier film having a laminating suitability and a good suitability for filling and packaging the contents, a laminated material and a packaging container using the same.

[0004]

As a result of various studies to solve the above-mentioned problems, the present inventor focused on a silane coupling agent, and firstly, on one side of a flexible plastic substrate. A thin film of an inorganic oxide, and further, a thin film of a silane coupling agent is provided on the thin film of the inorganic oxide, a transparent barrier film using the same, a laminated material using the same, and a packaging container are proposed. It was done. The present inventor further studied the above-mentioned transparent barrier film, a laminated material using the same, and a packaging container.As a result of various studies, when providing a thin film of a silane coupling agent, water containing a silane coupling agent was used. Focusing on providing a coating thin film using an alcohol-based composition, a thin film of an inorganic oxide is provided on one surface of a flexible plastic substrate, and the inorganic oxide film is further provided. On the thin film of the product, a coating thin film of a water / alcohol-based composition containing a silane coupling agent is provided to produce a transparent barrier film, and further, on the coating thin film surface of the transparent barrier film, At least a heat-sealing resin layer is laminated and laminated via an adhesive layer formed by a curing reaction between polyester polyol or polyether polyol and isocyanate. The packaging material was manufactured by using the laminated material to form a bag or a box, and various articles were filled and packaged in the packaging container. It has high barrier properties against gas, water vapor, etc., and also has excellent impact resistance, laminating strength, etc., has suitability for filling and packaging the contents, and has no cracks during post-processing and is extremely high. A transparent barrier film having post-processing suitability and further having sufficient microwave oven suitability even when the packaged product is microwaved, and having packaging suitability for various articles as a packaging material, and a laminated material using the same. The present invention has been completed by finding that a container for packaging and the like can be manufactured.

That is, according to the present invention, a thin film of an inorganic oxide is provided on one surface of a flexible plastic substrate, and a water / alcohol containing a silane coupling agent is provided on the thin film of the inorganic oxide. The present invention relates to a transparent barrier film provided with a coating thin film made of a roll-based composition, a laminated material 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 a transparent barrier film according to the present invention, a laminate material and a packaging container using the same will be described with reference to the drawings by way of examples. FIG. 1 shows a layer of the transparent barrier film according to the present invention. FIGS. 2 and 3 are schematic cross-sectional views showing the layer structure of a laminated material manufactured using the transparent barrier film according to the present invention. 5, FIG. 6, FIG. 7, and FIG. 8 are schematic plan views or perspective views showing the configuration of a packaging container formed from a bag using the laminated material using the transparent barrier film according to the present invention. FIG.

[0007] The transparent barrier film 1 according to the present invention comprises:
As shown in FIG. 1, a thin film 3 of an inorganic oxide is provided on one surface of a flexible plastic substrate 2, and a water containing a silane coupling agent is further provided on the thin film 3 of the inorganic oxide. It has a configuration in which a coating thin film 4 made of an alcohol-based composition is provided. Thus, the above examples are examples of the transparent barrier film according to the present invention, and are not limited thereto. For example, although not shown, a thin film of an inorganic oxide, a silane coupling agent The thin film or the like may be provided not only on one surface of the flexible plastic substrate but also on both surfaces thereof.

Next, a laminate manufactured using the transparent barrier film according to the present invention will be described with reference to a few examples. As the laminate according to the present invention, for example, as shown in FIG. An adhesive layer 5 formed on the surface of the coating thin film 4 of the transparent barrier film 1 shown in FIG. 1 by a curing reaction between polyester polyol or polyether polyol and isocyanate. A laminated material A obtained by laminating at least a heat-sealing resin layer 6 can be mentioned. As a laminated material according to the present invention, as shown in FIG. 3, the surface of the coating thin film 4 of the transparent barrier film 1 shown in FIG. 1 is coated with a polyester polyol or a polyether polyol and an isocyanate. At least a base film 7 is laminated via an adhesive layer 5 formed by a curing reaction with the base material, and further, a flexible plastic base material 2 or a base film constituting the transparent barrier film described above. A laminated material B obtained by laminating at least a heat-sealing resin layer 6 on any one of the layers 7 via the same adhesive layer 5 as described above can be mentioned. Thus, the above-mentioned examples are a few examples constituting the laminated material according to the present invention, and are not limited thereto. For example, in the present invention, although not shown, a base film In addition to the heat-sealing resin layer, etc., other base materials can be arbitrarily laminated according to the purpose of use, the contents to be filled and packaged, the distribution channel, the sales form, the use, etc. Can be designed and manufactured. In the present invention, the laminating positions of the base film, the heat-sealing resin layer, and other layers are arbitrarily laminated according to the purpose of use, application, and the like, and laminated materials of various forms are designed. It can be manufactured by In the present invention, the inorganic oxide thin film 3, the coating thin film 4 made of a water / alcohol-based composition containing a silane coupling agent, and the adhesive layer 5 are:
It is important that they are laminated adjacent to each other in this order, but the other base materials are arbitrarily laminated according to the purpose of use, application, etc., and various forms of laminated materials are designed. It can be manufactured.

Next, in the present invention, the structure of the packaging container according to the present invention, which is formed by using the above-mentioned laminated material to form a bag or a box, will be described. By way of example, a description will be given of a packaging container made from a bag or a box using the laminated material A shown in FIG. 2, 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 6 and 6 are superposed on each other, and then three sides of the outer peripheral edge are heat-sealed to form seal portions 8, 8 and 8. In this manner, the three-way seal type flexible packaging container C can be manufactured. Thus, in the above-mentioned three-way seal type flexible packaging container C, the contents are filled from the upper opening, and then the opening is heat-sealed to produce a packaged product. can do.

Next, as a packaging container according to the present invention, as shown in the schematic plan view of FIG. 5, for example, the above-mentioned laminated material A shown in FIG. 2 is used. Further, a paper base material is laminated on the flexible plastic base material constituting the above, and a heat-sealing resin layer is further formed on the paper base material to produce a laminated material. Using the laminated material, a blank plate 10 for forming a paper container having a predetermined crease 1 (indicated by a dotted line), a sticking portion 9 and the like is punched out and manufactured. As shown in the schematic perspective view of
The sticking portion 9 of the blank plate 10 is attached to the other side end 11 (FIG. 5).
), And the overlapped portion is heat-sealed to form a side end seal portion 12 to produce a body portion 13. Further, a lower portion of the body portion 13 is folded in a conventional manner. To form a bottom portion 14, and further heat-seal the upper portion in accordance with a conventional method to form a roof-type seal portion 1.
By forming No. 5, the roof-shaped paper packaging container D according to the present invention can be manufactured.

Further, as shown in the schematic plan view of FIG. 7, for example, the laminated material A shown in FIG. 2 is used as the packaging container according to the present invention.
On a flexible plastic substrate constituting the laminated material A,
Further, a paper base material is laminated, and further, a heat-sealing resin layer is formed on the paper base material to produce a laminated material, and the laminated material is used. A blank plate 10a for forming a rectangular paper container, which is capable of forming a cylindrical body, is punched and manufactured, and then, as shown in a schematic perspective view of FIG. The overlapping portion 9a is overlapped with the other side end 11a (shown in FIG. 7), and the overlapped portion is heat-sealed to form the side end seal 12a to form the cylindrical body 13a. The bottom portion 16a is formed by heat-sealing, for example, a cylindrical bottom plate 16 below the cylindrical body portion 13a to form a bottom seal portion 17; At the upper part of the cylindrical container 13a, for example, a cylindrical lid plate 20 having a drinking port 19 sealed with a peeling piece 18 is heathered. Upper sheet and Le - constitutes the lid portion 20a to form the pole tip 21, it is possible to produce a cylindrical paper can-shaped packaging containers D according to the present invention. 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 transparent barrier film, laminated material, packaging container and the like according to the present invention as described above will be described. As such materials, various materials can be used. it can. First, in the present invention, the material constituting the transparent barrier film according to the present invention will be described. First, as a flexible plastic substrate, a plastic film or sheet capable of holding an amorphous thin film of an inorganic oxide. Any type of resin can be used, for example, polyolefin resins such as polyethylene, polypropylene, and polybutene, (meth) acrylic resins, polyvinyl chloride resins, polystyrene resins, and polyvinylidene chloride resins. ,
Saponified ethylene-vinyl acetate copolymer, polyvinyl alcohol, polycarbonate resin, fluorine resin, polyvinyl acetate resin, acetal resin, polyester resin, polyamide resin, etc. Various resin films or sheets can be used. These resin films or sheets may be uniaxially or biaxially stretched, and have a thickness of about 10 to 200 μm, preferably 10 to 100 μm.
The m-th position is desirable. If necessary, the film or sheet of the resin may be coated with an anchor coat agent or the like and subjected to a surface smoothing treatment or the like.

Further, in the present invention, as the thin film of the inorganic oxide constituting the transparent barrier film, basically, any thin film in which a metal oxide is made amorphous can be used. For example, for example, silicon (S
i), aluminum (Al), magnesium (Mg),
Calcium (Ca), potassium (K), tin (Sn),
Sodium (Na), boron (B), titanium (Ti),
A thin film in which an oxide of a metal such as lead (Pb), zirconium (Zr), or 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 in which the above metal oxide is made amorphous can be referred to as a metal oxide, such as silicon oxide, aluminum oxide, and magnesium oxide.
For example, SiO _X, AlO _X, as such as MgO _X MO
_X (wherein, M represents a metal element, and the value of X is
The range differs depending on the metal element. ). The range of the value of X is silicon (S
i) is 0-2, and aluminum (Al) is 0-1.
5. Magnesium (Mg) is 0-1, calcium (C
a) is 0-1, potassium (K) is 0-0.5, tin (Sn) is 0-2, and sodium (Na) is 0-0.
5, boron (B) is 0-1,5, titanium (Ti) is
0-2, lead (Pb): 0-1, zirconium (Zr)
Can have a value in the range of 0 to 2 and yttrium (Y) can have a value in the range of 0 to 1.5. In the above, when X = 0,
It is a perfect metal, is not transparent and cannot be used at all, and the upper end of the range of X is a fully oxidized value. In the present invention, as a packaging material, generally, there are few examples of use other than silicon (Si) and aluminum (Al).
0 and aluminum (Al) having a value in the range of 0.5 to 1.5 can be used. In the present invention, the thickness of the inorganic oxide thin film as described above, depending on the type of metal used, or metal oxide, etc.,
For example, about 50-3000 °, preferably 100-1
It is desirable to form the film by arbitrarily selecting it within the range of about 000 °. Further, in the present invention, the inorganic oxide thin film is not limited to one layer of the inorganic oxide thin film, but may be a laminate of two or more layers. Can be used alone or as a mixture of two or more to form a thin film of an inorganic oxide mixed with different materials.

Next, a method of forming a thin film of an inorganic oxide on a flexible plastic substrate in the present invention will be described. Examples of the method include a vacuum deposition method, a sputtering method, and an ion plating method. Physical 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, the method for forming a thin film of an inorganic oxide will be specifically described. A vacuum evaporation method in which a metal oxide as described above is used as a raw material and heated to deposit on a flexible plastic substrate, Alternatively, an oxidation reaction deposition method in which a metal or metal oxide is used as a raw material, oxygen is introduced and oxidized to deposit on a flexible plastic substrate, and a plasma-assisted oxidation method in which an oxidation reaction is further assisted by plasma. An evaporation film can be formed by a reactive evaporation method or the like. Further, in the present invention, when forming a deposited film of silicon oxide,
The deposited film can be formed by a plasma enhanced chemical vapor deposition method using an organosiloxane as a raw material. In the present invention, when producing a transparent barrier film used for packaging material, mainly using a vacuum evaporation method, partially,
Plasma chemical vapor deposition may also be used.

In the present invention, a specific example of a method of forming a thin film of an inorganic oxide is shown in FIG. 9. FIG. 9 is a schematic structural view showing an example of a roll-up type vapor deposition machine. As shown in FIG. 9, in a vacuum chamber 111, a flexible plastic base material 113 unwound from an unwinding roll 112 is
After passing through the coating drum 114, the deposition chamber-11
5 where the evaporation source heated in the crucible 116 is evaporated and, if necessary, the oxygen outlet 11
7, the flexible plastic substrate 113 on the cooled coating drum 114 while ejecting oxygen or the like from the substrate.
A vapor-deposited inorganic oxide film is formed on the substrate through masks 118, 118, and the flexible plastic substrate 113 on which the vapor-deposited film is formed is fed into a vacuum chamber 111 to take up a roll 119. The flexible plastic substrate having a thin film of the inorganic oxide according to the present invention can be manufactured by winding the film.

FIG. 10 is a schematic configuration diagram illustrating an example of a plasma chemical vapor deposition apparatus illustrating a specific example of the plasma chemical vapor deposition method. As shown in FIG. 10, the vacuum chamber-2 of the plasma chemical vapor deposition apparatus 211
One surface of the flexible plastic base material 214 unreeled from the unwinding roll 213 arranged in the inside 12 is an auxiliary roll.
Are supplied at a constant speed through the cooling / electrode drum 216 and are supplied from the raw material volatile supply devices 217, 218 and 219 on the peripheral surface of the cooling / electrode drum 216, for example, an organic silicon compound, an oxygen gas, and an inert gas. Is introduced through the raw material supply nozzle 220, and a thin film of an inorganic oxide such as a deposited silicon oxide film is formed by the glow discharge plasma 221 on the flexible plastic substrate 214.
A predetermined voltage is applied to the cooling / electrode drum 216 from a power supply 222 disposed outside the vacuum chamber-212. A magnet 223 is disposed in the vicinity of 216 to promote the generation of plasma. Next, the flexible plastic substrate 214 on which a thin film of an inorganic oxide such as a silicon oxide vapor-deposited film is formed, is provided with an auxiliary roller. The transparent barrier film according to the present invention can be manufactured by winding the film on a winding roll 224 via a roll 215. In the figure,
225 represents a vacuum pump.

In the above, the thin film mainly composed of a deposited silicon oxide film as a thin film of an inorganic oxide is composed of a silicon compound having at least silicon and oxygen as constituent elements, and further has carbon or hydrogen as a trace constituent element. And at least one of the following elements, and has a thickness of 100 to 300:
It is preferably within the range of Å. Thus,
In the present invention, as the silicon oxide thin film as described above, an evaporated film formed from an organic silicon compound as a raw material and formed by a plasma chemical vapor deposition method using a low-temperature plasma generator or the like can be used. 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, etc. can be used . In the present invention, among the above-mentioned organosilicon compounds, the use of 1.1.3.3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material is advantageous in terms of handleability and formed deposited film. It is a particularly preferable raw material in view of its characteristics and the like. Further, in the above, as the low-temperature plasma generator, for example, a generator such as a high-frequency plasma, a pulse wave plasma, a microwave plasma, or the like can be used. In order to obtain the above, it is desirable to use a generator using a high-frequency plasma method.

Next, in the present invention, a silane coupling agent forming a coating thin film of a water / alcohol-based composition containing a silane coupling agent constituting a transparent barrier film includes a binary reactive compound. Organofunctional silane monomers having the formula:
γ-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane, γ-
Glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-
Aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane, γ-
One or more of aqueous solutions of aminopropylsilicone and the like can be used. In the silane coupling agent as described above, a functional group at one end of the molecule, usually, a chloro, alkoxy, or acetoxy group, or the like is hydrolyzed to form a silanol group (SiOH). The metal constituting the thin film of the substance, or an active group on the surface of the thin film of the inorganic oxide, for example, a functional group such as a hydroxyl group, by some action, for example, causes a reaction such as a dehydration condensation reaction, and the thin film of the inorganic oxide A silane coupling agent is modified on the surface by a covalent bond or the like, and a strong bond is formed on the surface of the inorganic oxide thin film of the silanol group itself by adsorption or hydrogen bonding. On the other hand, an organic functional group such as vinyl, methacryloxy, amino, epoxy, or mercapto at the other end of the silane coupling agent is formed on a thin film of the silane coupling agent. Reacts with substances constituting the agent layer, anchor coating agent layer, other layers, etc. to form a strong bond, and furthermore, the above-mentioned laminating adhesive layer, anchor coating agent layer, etc. Through
The heat-sealing resin layer is firmly and tightly bonded to increase the laminating strength, and thus, in the present invention,
This makes it possible to form a strong laminated structure having high laminate strength. In the present invention, utilizing the inorganic and organic properties of the silane coupling agent, a heat-sealing resin is formed via a thin film of an inorganic oxide and an adhesive layer or an anchor coating agent layer. It improves the tight adhesion with the layer, thereby increasing the laminating strength and the like.

According to the present invention, the water-alcohol-based composition containing the above-mentioned silane coupling agent is used as a core.
As a method of forming a thin film, a solvent and a diluent may be water (100%) or at least water, ethanol or isopropyl alcohol, which contains one or more of the above silane coupling agents. (IP
A) Alternatively, a water / alcohol-based composition containing a silane coupling agent is prepared by adding or dissolving or mixing a solvent or diluent consisting of a simple substance or a mixture of ethyl acetate or the like, and then adding The water / alcohol-based composition is coated on a thin film of inorganic oxide by, for example, roll coating, gravure coating, 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, whereby the coating thin film according to the present invention can be formed. In the above, when adjusting the water / alcohol-based composition containing the silane coupling agent, if necessary,
Additives such as a binder such as a resin, a stabilizer, a filler, a lubricant, an ultraviolet absorber, and the like can be optionally added.
In the above, the content of the silane coupling agent is about 0.05% to 10% by weight, preferably 0.1% by weight.
About 1% to 5% by weight is desirable, and the content of water is about 1.0% to 100% by weight, preferably
5.0 wt% to 75 wt% is desirable, and the content of alcohol is 0.5 wt% to 75 wt%,
Preferably, about 1.0% to 50% by weight is desirable.
In the present invention, by including water in the water-alcohol-based composition containing a silane coupling agent,
Functional groups such as alkoxy and chloro in the silane coupling agent are hydrolyzed to form silanol groups (Si-OH). Thus, the silanol groups and inorganic oxide are deposited on the surface of the deposited film. A dehydration-condensation reaction occurs with the existing functional group such as a hydroxyl group, and the silane coupling agent is modified by a covalent bond on the surface of the inorganic oxide vapor-deposited film. Further, the silanol group itself may be adsorbed on the deposited film of the inorganic oxide or bonded by hydrogen bonding. On the other hand, it has an organic functional group such as vinyl, methacryloxy, amino, epoxy, or mercapto at the other end of the silane coupling agent, and an adhesive for laminating used when laminating these organic functional groups. Reacts with an anchor coating agent and other materials constituting the layer to form a firm bond. As a result,
Desirable laminated material excellent in laminate strength between the thin film of inorganic oxide and a laminated material such as a heat-sealing resin layer, both of which are very strongly bonded via a silane coupling agent. It is possible to manufacture packaging containers and the like. It is most preferable that the coating thin film is formed as a monomolecular film by a silane coupling agent, for example. It is preferable that the film is formed with a thickness of μm.

Next, in the present invention, the polyester polyol or the polyether constituting the laminate according to the present invention.
As an adhesive layer formed by a curing reaction between terpolyol and isocyanate, for example, a polymer obtained by reacting a polyfunctional isocyanate with a hydroxyl group-containing compound, specifically, for example, Aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate and polymethylene polyphenylene polyisocyanate, or aliphatic such as hexamethylene diisocyanate and xylylene diisocyanate One-pack or two-pack polyurethane resins obtained by reacting a polyfunctional isocyanate such as polyisocyanate with a hydroxyl group-containing compound such as polyetherpolyol, polyesterpolyol, polyacrylatepolyol, etc. An adhesive composition containing a vehicle as a main component is used. Turkey - door, gravure co - door, Naifuko - door, Deppuko - door, Supureiko - door, the other co -
The adhesive layer constituting the laminated material according to the present invention can be formed by coating with a coating method and drying the solvent, diluent and the like. In the above, the thickness of the adhesive layer is preferably 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. Improve post-processing suitability such as bag processing,
This prevents cracks and the like from occurring in the inorganic oxide thin film during post-processing.

In the present invention, the adhesive layer formed by the curing reaction between the polyester polyol or the polyether polyol and the isocyanate constituting the laminated material according to the present invention is as follows. , JIS K6
No. 4 dumbbell according to No. 301 in an environment of 23 ° C. and 50% RH at 300 mm / min. Measured under the speed conditions of
Desirably, it has a tensile elongation of 300% to 550%. In the present invention, the tensile elongation of the above-mentioned adhesive layer is synergistic with the above-mentioned coating thin film and the like, and the inorganic oxide thin film, the coating thin film, the adhesive layer, the heat sheet and the like constituting the laminated material. This improves the tight adhesion with the conductive resin layer and the like, thereby preventing the occurrence of cracks and the like in the inorganic oxide thin film. In the above, if the tensile elongation is less than 300%, lack of flexibility,
In the post-processing such as laminating or bag making or box making, it is not preferable because cracks and the like are generated in the thin film of the inorganic oxide, and when the tensile elongation exceeds 550%, the flexibility becomes excessive, It is not preferable because it is inferior in tearing property, for example, inferior in opening property of the packaging container. In the present invention, if necessary, for example, a cellulose derivative such as nitrocellulose, and other binders may be optionally added to the polyurethane resin composition as described above. Can be done.

In the present invention, together with the above-mentioned adhesive layer, if necessary, for example, at the time of lamination, for example, an organic titanium-based anchor coating agent such as alkyl titanate, an isocyanate-based anchor coating agent, etc. Agents, polyethyleneimine-based anchor coating agents, polybutadiene-based anchor coating agents, and the like can be used. Thus, in the present invention, for example, roll coat, gravure coat,
Coating by knife coating, dip coating, spray coating or other coating methods, drying the solvent, diluent, etc., and then anchor coating with the anchor coating agent according to the present invention. An agent layer can be formed. In the above, the coating amount of the anchor coating agent is 0.1 to 5 g.
/ M ² (dry state). In the present invention, together with the above-mentioned adhesive layer, if necessary, for example, at the time of lamination, for example, polyurethane-based, polyester-based, polyamide-based, epoxy-based, poly (meth) acryl-based, polyvinyl acetate-based, polyolefin-based Or modified polyolefin, casein, wax, ethylene- (meth) acrylic acid copolymer, polybutadiene, etc. as a main component of the vehicle, various types such as a solvent type, an aqueous type, a non-solvent type, or a hot melt type. Can be used. In the present invention, for example, roll coating, gravure coating, knife coating, dip coating, spray coating, and other coating methods are used.
Then, the solvent, the diluent and the like are dried to form an adhesive layer using the adhesive for laminating according to the present invention. In the above, the coating amount of the adhesive for laminating is desirably about 0.1 to 6 g / m ² (dry state).

Next, in the present invention, the innermost layer of the laminated material,
Alternatively, as the heat-sealing resin constituting the heat-sealing resin layer forming the outermost layer, a resin film or sheet which can be melted by heat and fused together can be used. Specifically, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid Copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-
Methyl methacrylate copolymer, ethylene-propylene copolymer, methyl pentene polymer, polybutene polymer, polyolefin resin such as polyethylene or polypropylene, acrylic 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 100 μm.
μm is desirable.

Further, in the present invention, the base film has excellent mechanical, physical, chemical and other properties because it is a basic material when constituting a packaging container. In particular, a resin film or sheet having strength and toughness and having heat resistance can be used, and specifically, for example, a polyester resin, a polyamide resin, a polyaramid resin, Polyolefin resin, polycarbonate resin, polystyrene resin, polyacetal resin, fluorine resin,
Other tough resin films or sheets, etc. can be used. Thus, as the resin film or sheet, any one of an unstretched film and a stretched film stretched in a uniaxial or biaxial direction can be used. The thickness of the film is about 5 μm to 100 μm, preferably about 10 μm to 50 μm. In the present invention, the base film as described above is subjected to, for example, front printing or back printing by printing a desired printing pattern such as a character, a figure, a symbol, a picture, or a pattern by a normal printing method. It may be.

Next, in the present invention, as the above-mentioned substrate film, for example, various paper substrates constituting a paper layer can be used.
The paper base material is provided with shapeability, bending resistance, rigidity, etc., for example, strong size bleached or unbleached paper base material, or pure white roll paper, kraft paper, paperboard, A paper substrate such as a processed paper or the like can be used. In the above, the paper base constituting the paper layer has a basis weight of about 80 to
600 g / m ² , preferably about 100-200 g / m ²
It is desirable to use a material of about 450 g / m ² . Needless to say, in the present invention, a paper base constituting the paper layer and various resin films or sheets as the base films mentioned above can be used in combination.

Next, in the present invention, as a material constituting the laminated material according to the present invention, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene having a barrier property against water vapor, water and the like. Density polyethylene, polypropylene, film or sheet of resin such as ethylene-propylene copolymer, or, oxygen, polyvinylidene chloride having a barrier property against water vapor, etc.,
Film or sheet of resin such as polyvinyl alcohol, saponified ethylene-vinyl acetate copolymer, light-shielding obtained by adding a colorant such as pigment to the resin and other desired additives and kneading to form a film. Various colored resin films or sheets having properties can be used. These materials can be used alone or in combination of two or more. The thickness of the above-mentioned film or sheet is arbitrary, but usually 5 μm to 300 μm.
And more preferably about 10 μm to 100 μm.

In the present invention, since the packaging container is usually subjected to severe physical and chemical conditions, strict packaging suitability is required for the packaging material constituting the packaging container. And various conditions such as deformation prevention strength, drop impact strength, pinhole resistance, heat resistance, sealability, quality maintenance, workability, hygiene, etc. are required. Any material that satisfies the above conditions can be selected and used.Specifically, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, Ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid or methacrylic acid copolymer, Chillpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, poly (meth) acrylic resin, polyacrylonitrile resin, Polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin, polycarbonate resin, polyvinyl alcohol Resin, saponified ethylene-vinyl acetate copolymer, fluororesin,
It can be arbitrarily selected from known resin films or sheets such as diene resins, polyacetal resins, polyurethane resins, nitrocellulose and others. In addition, for example, a film such as cellophane, synthetic paper, or the like can be used. In the present invention, the above-mentioned film or sheet can be used in any of unstretched and uniaxially or biaxially stretched. The thickness is arbitrary, but is from several μm to 3 μm.
It can be used by selecting from a range of about 00 μm.
Further, in the present invention, the film or sheet may be any film such as an extruded film, an inflation film, or a coating film. In the present invention, any one of the layers constituting the laminated material according to the present invention may be formed by, for example, offset printing, gravure printing, silk screen printing, or any other desired method including characters, figures, patterns, symbols, etc. It goes without saying that a print pattern layer can also be formed.

Next, a method of manufacturing a laminated material using the above-mentioned materials in the present invention will be described.
For example, a wet lamination method, a dry lamination method, a solventless dry lamination method, an extrusion lamination method, a T-die extrusion molding method, a co-extrusion lamination method, an inflation method, It can be performed by an extrusion inflation method or the like. Thus, in the present invention, when performing the above-mentioned lamination, if necessary, a pretreatment such as a corona treatment or an ozone treatment can be performed on the film, and for example, an isocyanate-based (urethane) Series), polyethyleneimine series, polybutadiene series, organic titanium series etc.
Known pretreatments such as coating agents or adhesives for laminating such as polyurethane, polyacrylic, polyester, epoxy, polyvinyl acetate, cellulose, etc., anchor coating Agents, adhesives and the like can be used.

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, and it is folded or the two sheets are overlapped, and furthermore, the peripheral edge portion is formed. 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)
And the like can be manufactured, and in the present invention, a tube container and the like can 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, etc., or a zipper for opening and closing can be arbitrarily attached to the packaging container as described above.

Next, in the case of a liquid-filled paper container containing a paper substrate as a packaging container, for example, a laminated material in which a paper substrate is laminated is produced as a laminated material, and a desired paper container is produced therefrom. A blank plate is manufactured, and thereafter, a body, a bottom, a head and the like are manufactured using the blank plate to manufacture, for example, a liquid paper container of a brick type, a flat type or a gable-top type. be able to. Moreover, the shape can be manufactured by any of a rectangular container, a circular or other cylindrical paper can, and the like.

In the present invention, the packaging container manufactured as described above can be used for various foods and drinks, chemicals such as adhesives and adhesives, cosmetics, pharmaceuticals, miscellaneous goods such as chemical warmers, and various other products such as others. It is used for filling and packaging of articles. 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.

[0032]

EXAMPLES The present invention will be described more specifically with reference to examples. Example 1 First, as a silane coupling agent, (1). N-β
(Aminoethyl) -γ-aminopropyltrimethoxysilane, (2). N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane is used, and 1 part by weight of the silane coupling agent is mixed with water: isopropyl alcohol (IPA) = 1: 1. Dissolved in 100 parts by weight, each containing 2 types, concentration of about 1.0%
A silane coupling agent composition of wt was prepared. next,
Using these two types of silane coupling agent compositions, a biaxially stretched nylon film having a thickness of 15 μm and having a deposited film of silicon oxide having a thickness of 200 ° formed by chemical vapor deposition (CVD). Coating was performed on the surface of the deposited silicon oxide film having a thickness of 200 mm by using the roll coating method.
And then dried at 120 ° C. for 20 seconds to form a coating thin film (thickness, about 1.0 g / m ² , dry state) of the silane coupling agent composition. Was produced. A two-part curable polyurethane-based resin composed of polyester polyol and isocyanate is formed on a 7% ethyl acetate solution on the coated thin film surface of the silane coupling agent of the two kinds of transparent barrier films produced above. Using an adhesive, this is coated to a film thickness of 1 μm to form an adhesive layer, and then a low-density polyethylene is used on the surface of the adhesive layer, which is extruded to a thickness of 60 μm and coated. Thus, two types of laminated materials according to the present invention having the following layer configurations were produced. A biaxially stretched nylon film having a thickness of 15 μm, a vapor-deposited silicon oxide film having a thickness of 200 ° / a thin film coated with a silane coupling agent, an adhesive layer having a thickness of 1 μm, and a low-density polyethylene layer having a thickness of 60 μm. Using each laminated material, make a bag with a bag making machine
A plastic bag was manufactured. Next, the plastic bag produced above was filled with ham and sausage, and then the opening was heat-sealed to produce a filled and packaged product. However, no deterioration of the barrier properties was observed, and extremely good results were obtained.

Example 2 The two kinds of silane coupling agent compositions prepared in Example 1 were used, and the chemical vapor deposition (CVD) was used in the same manner as in Example 1 above. Thickness 2 of a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm and having a deposited silicon oxide film having a thickness of 200 °
A roll coat was applied to the surface of the deposited silicon oxide film of
Coating using the coating method and then at 120 ° C. for 2 hours.
After drying for 0 seconds, a coating thin film of the silane coupling agent composition (film thickness, about 1.0 g / m ² , dry state)
Was formed to produce two types of transparent barrier films according to the present invention. Next, the same two-part curable polyurethane-based resin as in Example 1 above, consisting of a 7% ethyl acetate solution, was adhered onto the silane coupling agent coated thin film surfaces of the two types of transparent barrier films produced above. Use the agent,
This was coated to a film thickness of 1 μm to form an adhesive layer, and then the low-density polyethylene was used on the surface of the adhesive layer while being melt-extruded to a thickness of 20 μm,
A μm low density polyethylene film was laminated. Furthermore,
The biaxially stretched polyethylene terephthalate film constituting the transparent barrier film is made of low-density polyethylene, extruded to a thickness of 100 μm, and laminated to form two types of the present invention having the following layer structure: Was manufactured. Low-density polyethylene layer having a thickness of 100 μm / bi-stretched polyethylene terephthalate film having a thickness of 12 μm, deposited silicon oxide film having a thickness of 200 mm / coating thin film of a silane coupling agent / adhesive layer having a thickness of 1 μm / thickness Extruded low-density polyethylene layer (adhesive layer) having a thickness of 20 μm / low-density polyethylene film having a thickness of 80 μm Using each laminated material produced above,
The laminated material is rolled and its overlapping edge is heat-welded to produce a tubular body for forming a tube, and then one end of the tubular body is injected using polypropylene. The neck was formed by molding, and a cap was screwed onto the neck to produce two types of tube containers. Next, the contents were filled from the other opening of the above tube container, and then the opening was heat-sealed to produce a tube-shaped packaged product. The above product had a high degree of barrier properties and was suitable for filling and packaging the contents.

Example 3 First, γ-glycidoxypropyltrimethoxysilane was used as a silane coupling agent, and 1 part by weight of the silane coupling agent was mixed with water: isopropyl alcohol (IPA) = 1: 1. The silane coupling agent composition having a concentration of about 1.0% by weight was dissolved in 100 parts by weight of a mixed solvent composed of No. 1 to prepare a silane coupling agent composition. Using the silane coupling agent composition prepared above, a vapor-deposited silicon oxide film having a thickness of 400 ° formed by physical vapor deposition (PVD) in the same manner as in Example 1 above. 12 μm thick biaxially oriented polyethylene terephthalate film thickness 4
The surface of the deposited silicon oxide film is coated with a roll coat method, dried at 120 ° C. for 20 seconds, and coated with a silane coupling agent composition (film thickness). , About 1.0 g / m ² , in a dry state) to produce a transparent barrier film according to the present invention. Next, on the transparent thin film coated with the silane coupling agent composition on the transparent barrier film produced above, a two-part curable polyurethane resin composed of polyetherpolyol and isocyanate of 7% ethyl acetate was used. Using an adhesive made of a solution, this is coated to a film thickness of 1 μm to form an adhesive layer, and then a low-density polyethylene is used on the surface of the adhesive layer, which is extruded to 80 μm and coated. Thus, a laminated material having the following layer configuration was manufactured. Thickness 12
μm bi-stretched polyethylene terephthalate film, 400 Å thick silicon oxide deposited film / coating thin film with silane coupling agent composition / 1 μm thick adhesive layer / 80 μm thick low density polyethylene layer Using each of the produced laminated materials, a three-sided seal-type plastic bag was produced by a bag making machine. Next, the plastic bag produced above was filled with ham and sausage, and then the opening was heat-sealed to produce a filled and packaged product. However, no deterioration of the barrier properties was observed, and extremely good results were obtained.

Example 4 Using the silane coupling agent composition prepared in Example 3 above, a thickness formed by physical vapor deposition (PVD) in the same manner as in Example 1 above. 200Å
A 15 μm-thick biaxially stretched nylon film having an aluminum oxide vapor-deposited film was coated on the surface of a 200-mm-thick aluminum oxide vapor-deposited film by a roll coating method. To form a coating thin film (film thickness, about 1.0 g / m ² , dry state) of the silane coupling agent composition,
A transparent barrier film according to the present invention was manufactured. On the coated thin film surface of the silane coupling agent composition of the transparent barrier film produced above, an adhesive consisting of a 7% ethyl acetate solution of a two-part curable polyurethane resin as in Example 3 was used. This was coated to a film thickness of 1 μm to form an adhesive layer, and then a low-density polyethylene was used on the surface of the adhesive layer to form a film having a thickness of 20 μm.
While being extruded into a low-density polyethylene film having a thickness of 60 μm, the laminate was extruded and laminated to produce a laminated material according to the present invention having the following layer constitution. 15 μm thick biaxially stretched nylon film, 200 ° thick aluminum oxide deposited film / coated thin film of silane coupling agent / 1 μm thick adhesive layer / 20 μm thick extruded low density polyethylene layer (adhesive Layer) / Low-density polyethylene film having a thickness of 60 μm Using each of the laminates produced above, a three-sided seal-type plastic bag was produced by a bag making machine. Next, the plastic bag prepared above was filled with a liquid seasoning, and then the opening was heat-sealed to produce a filled packaged product. No deterioration of the properties was observed, and very good results were obtained.

COMPARATIVE EXAMPLE 1 A thickness of 20 formed by chemical vapor deposition (CVD)
A 15 μm thick biaxially stretched nylon film having a 0 ° silicon oxide deposited film was coated on a 200 ° silicon oxide deposited film surface with the same two-part curable polyurethane resin 7% ethyl acetate as in Example 1 above. Using an adhesive made of a solution, this is coated to a film thickness of 1 μm to form an adhesive layer. Then, low-density polyethylene is used on the surface of the adhesive layer, which is extruded to a thickness of 60 μm. To produce a laminated material having the following layer configuration. A biaxially stretched nylon film having a thickness of 15 μm, a vapor-deposited film of silicon oxide having a thickness of 200 mm / an adhesive layer having a thickness of 1 μm / a low-density polyethylene layer having a thickness of 60 μm. A three-sided seal-type plastic bag was manufactured by a machine. Next, the plastic bag produced above was filled with ham and sausage, and then the opening was heat-sealed to produce a filled packaging product.

COMPARATIVE EXAMPLE 2 A thickness of 20 formed by chemical vapor deposition (CVD)
200 μm thick biaxially oriented polyethylene terephthalate film having a thickness of 12 μm and having a deposited film of 0 ° silicon oxide
The same 2 as in Example 1 above was applied to the surface of the deposited silicon oxide film
An adhesive consisting of a 7% ethyl acetate solution of a liquid-curable polyurethane-based resin is used and coated to a thickness of 1 μm to form an adhesive layer. Then, low-density polyethylene is coated on the adhesive layer surface. A low-density polyethylene film having a thickness of 80 μm was extruded and laminated while being melt-extruded to a thickness of 20 μm. Further, a low-density polyethylene was used on the other surface of the biaxially stretched polyethylene terephthalate film laminated as described above, and a thickness of 100 μm was used.
The laminated material having the following layer constitution was manufactured by extruding and laminating the laminate. Low-density polyethylene layer having a thickness of 100 μm / double-stretched polyethylene terephthalate film having a thickness of 12 μm / a deposited film of silicon oxide having a thickness of 200 ° / thickness of 1
μm adhesive layer / 20 μm-thick extruded low-density polyethylene layer (adhesive layer) / 80 μm-thick low-density polyethylene film The laminated material produced above is used. The portion is heat-welded to produce a tubular body for forming a tube, and then, at one end of the tubular body, a neck is formed by injection molding using polypropylene. A cap was screwed onto the neck to produce two types of tube containers. Next, the contents were filled from the other opening of the above tube container, and then the opening was heat-sealed to produce a tube-shaped packaged product.

COMPARATIVE EXAMPLE 3 Thickness of 40 Formed Using Physical Vapor Deposition (PVD)
12 μm-thick biaxially stretched polyethylene terephthalate film having a thickness of 0 ° and a thickness of 400 mm
The same 2 as in Example 3 was applied to the surface of the deposited silicon oxide film
An adhesive consisting of a 7% ethyl acetate solution of a liquid-curable polyurethane-based resin is used and coated to a thickness of 1 μm to form an adhesive layer. Then, low-density polyethylene is coated on the adhesive layer surface. This was extruded to 80 μm and coated. Biaxially oriented polyethylene terephthalate film having a thickness of 12 μm and a vapor-deposited silicon oxide film having a thickness of 400 ° / thickness of 1 μm
Adhesive layer / Low-density polyethylene layer having a thickness of 80 μm Using the laminated material produced above, a three-sided seal-type plastic bag was produced by a bag making machine. Next, the plastic bag produced above was filled with ham and sausage, and then the opening was heat-sealed to produce a filled packaging product.

COMPARATIVE EXAMPLE 4 A thickness of 20 formed by physical vapor deposition (PVD)
15 μm thick with a deposited film of 0 ° aluminum oxide
An adhesive consisting of a 7% ethyl acetate solution of the same two-component curable polyurethane resin as used in Example 3 above was used on the surface of the biaxially stretched nylon film of aluminum oxide having a thickness of 200.degree. An adhesive layer is formed by coating to a thickness of 1 μm, and then a low-density polyethylene film is extruded to a thickness of 20 μm while a low-density polyethylene film having a thickness of 60 μm is extruded. Lamination was performed to produce a laminated material having the following layer configuration. 15 μm thick biaxially oriented nylon film, thickness 200
蒸 着 Aluminum oxide deposited film / Adhesive layer 1 μm thick / Extruded polyethylene layer 20 μm thick / 60 μm thick
m low-density polyethylene film Using the laminated material produced as described above, a three-sided seal-type plastic bag was produced by a bag making machine. Next, the plastic bag produced above was filled with a liquid seasoning, and then the opening was heat-sealed to produce a filled packaging product.

EXPERIMENTAL EXAMPLE 1 The laminated materials manufactured in Examples 1 to 4 and the laminated materials manufactured in Comparative Examples 1 to 4 were used. In Examples 1 to 4, the silane coupling agent was used. The surface of the coating thin film of the composition and the surface of the low-density polyethylene layer or film having a thickness of 60 or 80 μm, and those of Comparative Examples 1 to 4 are those of silicon oxide or 200 ° having a thickness of 200 ° or 400 °. A laminate strength test and a tear test were conducted on the surface of the aluminum vapor-deposited film and the surface of the low-density polyethylene layer or film having a thickness of 60 or 80 μm. Lamine above
The strength test was performed using a peel tester (Model name, Tensilon universal tester manufactured by Orientec Co., Ltd.)
The test was performed under the conditions of a width of 5 mm, a peeling angle of 90 degrees, 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.

[0041]

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

As shown in Table 1 above, those of Examples 1 to 4 have remarkably higher laminating strength than those of Comparative Examples 1 to 4, indicating that the silane coupling agent composition It was found that the peel strength was improved by forming the coating thin film. Also, the tearability was good. On the other hand, those of Comparative Examples 1 to 4 were not preferable because the laminating strength was not so improved.

EXPERIMENTAL EXAMPLE 2 Further, the laminated materials manufactured in Examples 1 to 4 and the laminated materials manufactured in Comparative Examples 1 to 4 were further subjected to bag making or box making. The following data was measured for the manufactured 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.
Matran (PERMATRAN)]. The above measurement results are shown in Table 2 below.

[0044]

[Table 2] 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 4 were generally good in oxygen permeability and water vapor permeability, while those of Comparative Examples 1 to 4 were excellent. Four were inferior.

[0046]

As is apparent from the above description, the present invention first provides a thin film of an inorganic oxide on one surface of a flexible plastic substrate, On top, a transparent barrier film provided with a thin film of a silane coupling agent, a laminated material using the same, and a container for packaging are proposed.
In providing a thin film of a silane coupling agent, attention was paid to providing a coating thin film using a water / alcohol-based composition containing a silane coupling agent. On one surface, a thin film of an inorganic oxide is provided, and a coating thin film of a water / alcohol-based composition containing a silane coupling agent is further provided on the thin film of the inorganic oxide to form a transparent barrier film. And furthermore,
At least a heat sealing property is formed on the coating thin film surface of the transparent barrier film via an adhesive layer formed by a curing reaction between polyester polyol or polyether polyol and isocyanate. A laminated material is manufactured by laminating the resin layers, and further, a packaging container is manufactured by bag making or box making using the laminated material, and various articles are filled and packaged in the packaging container. Oxygen gas, with excellent transparency,
It has high barrier properties against water vapor, etc., furthermore, it has excellent impact resistance, excellent laminating strength of the laminated material, has suitability for preserving the contents, and has no cracks during post-processing,
A transparent barrier film having extremely high post-processing suitability, and further having sufficient microwave oven suitability even when the packaged product is subjected to microwave oven, and having packaging suitability for various articles as a packaging material. Laminated materials, packaging containers and the like can be manufactured.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing a layer configuration of a transparent barrier film according to the present invention.

FIG. 2 is a schematic cross-sectional view showing a layer structure of a laminated material manufactured using the transparent barrier film according to the present invention.

FIG. 3 is a schematic cross-sectional view showing a layer configuration of a laminated material manufactured using the transparent barrier film according to the present invention.

FIG. 4 is a schematic perspective view showing a configuration of a packaging container formed by bag making or box making using a laminated material using the transparent barrier film according to the present invention.

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

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

FIG. 7 is a schematic plan view showing the configuration of a packaging container formed from a bag or a box using a laminated material using the transparent barrier film according to the present invention.

FIG. 8 is a schematic perspective view showing the configuration of a packaging container made from a bag or a box using a laminated material using the transparent barrier film according to the present invention.

FIG. 9 is a schematic configuration diagram illustrating an example of a roll-up type vapor deposition machine.

FIG. 10 is a schematic configuration diagram illustrating an example of a plasma chemical vapor deposition apparatus.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Transparent barrier film 2 Flexible plastic base material 3 Inorganic oxide thin film 4 Coating thin film 5 Adhesive layer 6 Heat-sealing resin layer 7 Base film 8 Seal part 9 Adhering part 10 Paper Blank plate for forming container 11 Side end 12 Side seal 13 Body 14 Bottom 15 Roof seal 9a Adhering portion 10a Blank plate for forming paper container 11a Side end 12a Side end seal 13a Cylindrical body 16 Cylindrical bottom plate 16a Bottom 17 Bottom seal 18 Peeling piece 19 Drinking mouth 20 Cylindrical lid plate 20a Lid 21 Upper seal 111 Vacuum chamber 112 Unwinding roll Roll 113 Flexible plastic substrate 114 Coating drum 115 Deposition chamber 116 Crucible 117 Oxygen outlet 118 Mask 119 Winding roll 211 Plasma Vapor deposition device 212 Vacuum chamber 213 Unwinding roll 214 Flexible plastic substrate 215 Auxiliary roll 216 Cooling / electrode drum 217, 218, 219 Raw material volatile supply device 220 Raw material supply nozzle 221 Glow discharge plasma 222 Power supply 223 Magnet 224 Take-up roll 225 Vacuum pump A Laminated material B Laminated material C Three-way seal type soft packaging container D Roof type paper packaging container E Cylindrical paper can packaging container l Folding rule

──────────────────────────────────────────────────の Continued on front page (51) Int.Cl. ⁶ Identification symbol FI C23C 16/40 C23C 16/40 // A61J 1/10 C08J 7/04 CFDM C08J 7/04 CFD A61J 1/00 331C (72) Inventor Hideki Kurokawa 1-1-1 Ichigaya Kagacho, Shinjuku-ku, Tokyo Inside Dai Nippon Printing Co., Ltd.

Claims (10)

[Claims] 1. A method according to claim 1, wherein one side of the flexible plastic substrate is
A transparent barrier comprising: a thin film of an inorganic oxide; and a coating thin film of a water / alcohol-based composition containing a silane coupling agent on the thin film of the inorganic oxide. the film. 2. The method according to claim 1, wherein the flexible plastic substrate comprises a biaxially stretched nylon film or a biaxially stretched polyethylene terephthalate film.
4. The transparent barrier film described in 1. above. 3. The transparent barrier film according to claim 1, wherein the inorganic oxide thin film comprises an inorganic oxide vapor-deposited film. 4. The transparent barrier film according to claim 1, wherein the inorganic oxide thin film comprises an inorganic oxide vapor-deposited film formed by a chemical vapor deposition method. 5. The transparent barrier film according to claim 1, wherein the deposited film of the inorganic oxide comprises a deposited film of silicon oxide or aluminum oxide. 6. One side of a flexible plastic substrate,
A thin film of an inorganic oxide is provided, and a coating thin film of a water / alcohol-based composition containing a silane coupling agent is provided on the thin film of the inorganic oxide.
At least a heat-sealing resin layer is laminated on the thin film through an adhesive layer formed by a curing reaction between polyester polyol or polyetherpolyol and isocyanate. A laminated material characterized by becoming. 7. One side of a flexible plastic substrate,
A thin film of an inorganic oxide is provided, and a coating thin film of a water / alcohol-based composition containing a silane coupling agent is provided on the thin film of the inorganic oxide.
At least a substrate film is laminated on the thin film via an adhesive layer formed by a curing reaction between polyester polyol or polyether polyol and isocyanate. A laminate comprising at least a heat-sealing resin layer laminated on one of a flexible plastic substrate and a substrate film. 8. The adhesive layer is formed with a No. 4 dumbbell according to JIS K6301 under an environment of 23 ° C. and 50% RH.
0 mm / min. 300% to 5
The laminate according to claim 6 or 7, wherein the laminate has a tensile elongation of 50%. 9. A method according to claim 1, wherein one side of the flexible plastic substrate is
A thin film of an inorganic oxide is provided, and a coating thin film of a water / alcohol-based composition containing a silane coupling agent is provided on the thin film of the inorganic oxide.
At least a heat-sealing resin layer is laminated on the thin film through an adhesive layer formed by a curing reaction between polyester polyol or polyetherpolyol and isocyanate. A packaging container characterized by being made from a laminated material and made into a bag or a box. 10. A water / alcohol-based composition containing a silane coupling agent on an inorganic oxide thin film provided on one surface of a flexible plastic base material. A coating thin film made of a material is further provided, and an adhesive layer is formed on the coating thin film by a curing reaction between polyester polyol or polyether polyol and isocyanate. , At least, laminate the base film, further, on one of the above-mentioned flexible plastic base material or base film,
A packaging container characterized by using a laminated material obtained by laminating at least a heat-sealing resin layer, and making the bag or box.