JP2000233468A - Laminate material and packing container using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate material having excellent transparency and high barrier properties against oxygen gas or steam, rich in aroma retentivity, impact resistance, thrust resistance, preservability of content or the like, having post-processing aptitude and excellent laminate strength and good in the filling and packing aptitude of content, in particular, a liquid seasoning and a packing container using the same. SOLUTION: In a laminate material, at least two or more membranes 2 comprising inorg. oxide are superposed on one surface of a nylon film 1 and a coating membrane comprising a primer compsn. containing a silane coupling agent or a polyester resin compsn. is provided on the membrane 2 and at least a heat-sealable resin layer 4 is laminated on the coating membrane 3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated material and a packaging container using the same, and more particularly, to transparency,
Excellent in barrier properties against oxygen gas, water vapor, etc., fragrance retention, impact resistance, piercing resistance, laminating strength, preservability against contents, etc., food packaging field, pharmaceutical packaging field, detergent,
Shampoos, oils, and various articles in the non-food field such as toothpaste, in particular, filling and packaging suitability for liquid seasonings such as dressing, oil, soy sauce, miso, sauce, vinegar, mayonnaise, Further, the present invention relates to a laminated material having microwave oven suitability and excellent post-process suitability, and a packaging container using the same.

[0002]

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

[0003]

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

[0004]

As a result of various studies to solve the above problems, the present inventor has found that it has excellent barrier properties against oxygen gas, water vapor, etc., impact resistance, puncture resistance, etc. Focusing on a biaxially stretched nylon film rich in elasticity, multi-layering of inorganic oxide thin films, silane coupling agents having organic and inorganic properties, polyurethane resins having extensibility, polyester resins, etc. On one side of the axially stretched nylon film, at least two or more inorganic oxide thin films are laminated to form a multilayer, and a primer composition containing a silane coupling agent is further provided on the inorganic oxide thin film. A coating thin film made of a product or a polyester-based resin composition, and further, at least a heat-sealing resin layer is laminated on the coating thin film to produce a laminated material. A packaging container is manufactured by bag-making or box-making using the laminated material, and then the content is packed in the packaging container, particularly, a liquid or viscous content such as a liquid seasoning. As a result, it has excellent transparency, high barrier property against oxygen gas or water vapor, etc., and also has excellent fragrance retention, impact resistance, piercing resistance, laminating strength, etc. It has excellent preservability to liquid or viscous contents, has no cracks during post-processing, has extremely high post-processing suitability, and even if the packaged product is subjected to a microwave oven, it can be sufficiently microwaved. The present invention has been completed by finding that a laminated material having aptitude and suitability for filling and packaging various articles as a packaging material and a packaging container and the like using the same can be produced.

That is, in the present invention, at least two layers of inorganic oxide thin films are provided on one surface of a nylon film, and a silane coupling agent is further provided on the inorganic oxide thin film. A coating thin film of a primer composition or a polyester-based resin composition containing the coating film, and further, at least
The present invention relates to a laminated material characterized by laminating a sealable resin layer and a packaging container using the laminated material.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. First, the configuration of the laminated material according to the present invention and the 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 is formed by laminating two or more inorganic oxide thin films 2 and 2 on one surface of a nylon film 1 to form a multilayer. A coating thin film 3 of a primer composition or a polyester resin composition containing a silane coupling agent on the inorganic oxide thin film 2;
Furthermore, at least on the coating thin film 3,
The basic structure is that the heat-sealing resin layer 4 is laminated. Further, as another example of the laminated material according to the present invention, as shown in FIG.
In the laminated material A shown in FIG. 1, between the coating thin film 3 and the heat-sealing resin layer 4, an anchor coating agent layer 5 or a laminating adhesive layer 5a is provided. Through
At least a laminated material B obtained by laminating the heat-sealing resin layer 4 can be used. Thus, the above-mentioned examples are a few examples constituting the laminated material according to the present invention, and the present invention is not limited thereto.For example, in the present invention, although not illustrated, In addition to the heat-sealing resin layer, etc., other base materials may be arbitrarily laminated according to the purpose of use, the contents to be filled and packaged, the distribution channel, the sales form, the use, etc. It is possible to design and manufacture a laminated material. In the present invention, 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, and an anchor coating agent layer, or
It is important that the adhesive layer for laminating is laminated adjacent to each other in this order in order to exhibit the function and effect such as close adhesiveness. Purpose,
Depending on the application or the like, various types of laminated materials can be designed and manufactured by arbitrarily laminating.

Next, in the present invention, the structure of the packaging container according to the present invention, which is 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 transparent resin layers 4 and 4 are overlapped with each other, and then the three sides of the outer peripheral edge are heat-sealed to form the seal portions 6, 6, and the present invention. , A 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 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 a schematic perspective view of FIG. The sealing resin layers 4 and 4 are superimposed on each other with the surfaces thereof facing each other. , A soft packaging container D of the two-way seal type can be manufactured. Thus, in the above two-way seal type flexible packaging container D,
As above, fill the contents from the opening above,
Thereafter, the opening can be heat-sealed to produce various packaged products. 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 laminated material according to the present invention, as a nylon film constituting a packaging container, is excellent in impact resistance, puncture resistance, etc., rich in toughness, and furthermore, the amorphous nature of the inorganic oxide Any polyamide-based resin film or sheet capable of holding a thin film can be used. Specifically, for example, nylon 46, nylon 6, nylon 66, nylon 610, nylon 612,
Various polyamide resin (nylon) films or sheets such as nylon 7, nylon 11, nylon 12, and the like can be used. The film or sheet of the polyamide resin (nylon) can be formed in a normal or biaxial direction by a normal biaxial stretching method such as a tenter system or a tuber system. It is desirable to use a stretched biaxially stretched polyamide resin (nylon) film or sheet, and its film thickness is about 5 to 200 μm, preferably 10 to 5 μm.
About 0 μm is desirable. The polyamide-based resin film or sheet can be subjected to a surface smoothing treatment by coating with an anchor coating agent or the like, if necessary. A surface treatment such as a discharge treatment, an ozone treatment, a flame treatment, or 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, the product according to the present invention
To explain the inorganic oxide thin film constituting the layer material,
Such inorganic oxide thin films basically consist of metal oxides.
Any amorphous thin film can be used.
Yes, for example, silicon (Si), aluminum (A
l), magnesium (Mg), calcium (Ca),
Lithium (K), tin (Sn), sodium (Na), e
U (B), titanium (Ti), lead (Pb), zirconium
Metal oxides such as aluminum (Zr) and yttrium (Y)
Morphus (amorphous) thin film can be used
You. As a material suitable for packaging materials,
Oxides of metals such as silicon (Si) and aluminum (Al)
Amorphous thin films can be mentioned.
You. Thus, oxides of the above metals are converted to amorphous (amorphous)
Quality) thin film is made of silicon oxide, aluminum oxide, acid
Metal oxides such as magnesium oxide
The notation is, for example, SiO_X, AlO_X, Mg
O_XMO as in _X(Where M is a metal element
And the value of X varies depending on the metal element.
Become. ). Also, as the range of the value of X described above,
Is silicon (Si) 0-2, aluminum (Al)
Is 0-1.5, magnesium (Mg) is 0-1,
Lucium (Ca) is 0-1, potassium (K) is 0
0.5, tin (Sn): 0-2, sodium (Na)
Is 0 to 0.5, boron (B) is 0 to 1, 5, titanium
(Ti): 0-2, Lead (Pb): 0-1, Zirconi
Um (Zr) is 0-2, yttrium (Y) is 0-2
Values can be in the range of 1.5. In the above,
If X = 0, it is completely metal, not transparent,
Cannot be used, and the upper limit of the range of X is
It is the value oxidized to. In the present invention, the packaging material
In general, silicon (Si), aluminum (A
Except for l), the examples used are poor and silicon (Si)
Is 1.0 to 2.0, and aluminum (Al) is 0.5
A value in the range of ~ 1.5 can be used.

In the present invention, as the inorganic oxide thin film, not only the above-described inorganic oxide thin film is formed in one layer but also at least two or more inorganic oxide thin films are laminated. In this method, a thin film of an inorganic oxide having a multilayer structure is used. Thus, in the present invention, a method of forming a film in which at least a thin film of an inorganic oxide is overlaid on a nylon film in two or more layers will be described.
Physical vapor deposition methods such as a sputtering method and an ion plating method (Physical Vapor Depos)
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.
position method, CVD method) and the like. In the present invention, to further explain the film-forming method, for example, using a metal oxide as a raw material, 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 the film in the range of about 2000 °, preferably about 100 to 1000 °. Thus, an inorganic oxide having a multilayer structure in which two or more inorganic oxide thin films are stacked and multilayered is formed. The thickness of the oxide thin film is 1
About 00-4000Å, preferably 120-2000Å
The position is the desired one.

In the present invention, a specific example of a film forming method in which an inorganic oxide thin film is laminated in two or more layers will be described. FIG. 5 is a schematic structural diagram showing an example of a roll-up type vacuum evaporator. It is. As shown in FIG.
1, a nylon film 113 fed from an unwinding roll 112 passes through a coating drum 114,
Enter the deposition chamber-115 where the crucible 11
6. Evaporate the heated source in step 6 and, if necessary,
While ejecting oxygen or the like from the oxygen outlet 117, an inorganic oxide deposition film is formed on the cooled nylon film 113 on the coating drum 114 via the masks 118, 118, and then deposited. The nylon film 113 having the film formed thereon is fed into the vacuum chamber 111, and then wound up on a take-up roll 119, whereby the nylon film 113 having a thin film of an inorganic oxide can be manufactured. In the present invention, the above-described film formation is repeated or, although not shown, the above-mentioned winding vacuum evaporator is connected in two or more to continuously evaporate. ,
An inorganic oxide thin film having a multilayer structure in which two or more inorganic oxide thin films are stacked to form a multilayer structure can be formed.

Further, in the present invention, a specific example of a film formation method in which an inorganic oxide thin film is laminated into two or more layers by the above-described plasma chemical vapor deposition method is shown in FIG.
1 is a schematic configuration diagram illustrating an example of a plasma chemical vapor deposition apparatus. As shown in FIG.
The 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, a nylon film having a thin film of an inorganic oxide can be produced. Thus, in the present invention, the film formation as described above is repeated or, although not shown, the above-described film formation is performed. By connecting two or more such plasma enhanced chemical vapor deposition apparatuses and depositing continuously,
An inorganic oxide thin film having a multilayer structure in which two or more inorganic oxide thin films are stacked to form a multilayer structure can be formed. In the drawing, reference numeral 225 denotes a vacuum pump.

Further, in the present invention, as a film forming method for laminating two or more inorganic oxide thin films, the above-mentioned physical vapor deposition methods such as a vacuum deposition method, a sputtering method and an ion plating method are used. (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 forming an inorganic oxide thin film composed of both layers into two or more layers to form a film. It is also possible to produce a thin film of an inorganic oxide having a laminated structure as described above. That is, although not shown, first, using the above-mentioned winding vacuum evaporation machine,
Then, a second inorganic oxide thin film is formed on the inorganic oxide thin film using the above-described plasma chemical vapor deposition apparatus, and the first and second inorganic oxide thin films are formed. With the inorganic oxide thin film of No. 2, the inorganic oxide thin film having a multilayer structure in which two or more inorganic oxide thin films are stacked can be formed. In the above, the order of film formation may be any, for example, first, film formation using a roll-up vacuum evaporation machine, then may be formed using a plasma chemical vapor deposition apparatus, Film formation may be performed in the reverse order.

In the above, the thin film mainly composed of a deposited silicon oxide film as the inorganic oxide thin film is made of a silicon compound containing at least silicon and oxygen as constituent elements,
Further, it is preferable that one or more elements of carbon or hydrogen are contained as trace constituent elements, and that the film thickness is in the range of 50 to 500 °. Thus, in the present invention, as the silicon oxide thin film as described above, an organic silicon compound is used as a raw material, and a vapor deposition film formed by a plasma chemical vapor deposition method using a low-temperature plasma generator or the like is used. be able to. In the above, as the organic silicon compound, for example, 1.1.3.3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethyl Silane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane,
Phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, and the like can be used. In the present invention, among the above-mentioned organosilicon compounds, the use of 1.1.3.3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material is advantageous in terms of handleability and formed deposited film. It is a particularly preferable raw material in view of its properties and the like. Further, in the above, as the low-temperature plasma generator, for example, a high-frequency plasma, a pulse wave plasma, a microwave plasma or the like generator may be used.
In the present invention, in order to obtain highly active and stable plasma, it is desirable to use a generator using a high-frequency plasma method.

Next, in the present invention, a coating thin film comprising a primer composition containing a silane coupling agent, which constitutes the laminated material according to the present invention, will be described. First, a primer composition containing a silane coupling agent Specifically, a polyurethane resin composition containing a silane coupling agent and a filler, or a water / alcohol composition containing a silane coupling agent can be used. In the above, as the silane coupling agent constituting the polyurethane resin composition, an organic functional silane monomer having a binary reactivity can be used. For example, γ-chloropropyltrimethoxysilane, vinyltrichlorosilane , Vinyltriethoxysilane, vinyl-tris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane , Vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β
(Aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane,
One or more of aqueous solutions of bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane and γ-aminopropylsilicone can be used.
The above-mentioned silane coupling agent hydrolyzes a functional group at one end of the molecule, usually, a chloro, alkoxy, or acetoxy group, and a silanol group (SiOH)
Forming a thin film of an inorganic oxide,
Alternatively, active groups on the surface of the inorganic oxide thin film, for example,
By a certain action with a functional group such as a hydroxyl group, for example, a reaction such as a dehydration condensation reaction is caused, and the silane coupling agent is modified on the surface of the inorganic oxide thin film by a covalent bond or the like. A strong bond is formed on the surface of the inorganic oxide thin film by adsorption, hydrogen bonding, or the like. On the other hand, vinyl, methacryloxy,
An organic functional group such as amino, epoxy, or mercapto is formed on a thin film of the silane coupling agent, for example, an adhesive layer for a laminate, an anchor coating agent layer, other layers, etc. Reacts with the substances constituting 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 to form a thin film of an inorganic oxide, a laminating adhesive layer or an anchor core.
Through the agent layer, the adhesiveness to the heat-sealing resin layer is improved, thereby increasing the laminate strength and the like.

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

Thus, in the present invention, the polyurethane resin composition may be a polyurethane resin,
30% by weight, silane coupling agent, 0.05 to
About 10% by weight, preferably 0.1% to 5% by weight
%, Filler 0.1-20% by weight, preferably 1-1
It is added at a ratio of about 0% by weight, and if necessary, additives such as a stabilizer, a curing agent, a cross-linking agent, a lubricant, an ultraviolet absorber, etc. are optionally added, and a solvent, a diluent, etc. are added. The polyurethane resin composition is prepared by mixing well. Thus, in the present invention, the above-mentioned polyurethane-based resin composition is, for example, roll-coated, gravure-coated,
Coating is performed on the inorganic oxide thin film by knife coating, dip coating, spray coating, or other coating methods, and then the coating film is dried to remove the solvent, diluent, and the like. Thus, the coating thin film according to the present invention can be formed. In the present invention, the thickness of the coating thin film made of the polyurethane resin composition is, for example, about 0.01 to 50 μm, preferably about 0.1 to 50 μm.
About 1 to 5 μm is desirable. In the present invention, the polyurethane-based resin composition may further include, if necessary, for example, a cellulose derivative such as nitrocellulose,
Other binders can be optionally added.

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

Next, in the present invention, a coating thin film made of a polyester resin composition constituting a laminate according to the present invention will be described. 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 according to the present invention can be melted by heat and fused to each other. Resin films or sheets can be used, and 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 Polyolefin resin such as pentene polymer, polybutene polymer, polyethylene or polypropylene Acid-modified polyolefin resin modified with unsaturated carboxylic acid such as luic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, polyvinyl acetate resin, poly (meth) acrylic resin, polyvinyl chloride resin And other resin films or sheets 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 preferably about 5 μm to 300 μm, more preferably about 10 μm to 150 μm.

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, the above linear low-density polyethylene and an ethylene / α-olefin copolymer polymerized using a metallocene catalyst are used, and they are co-extruded or laminated in two or more layers by tandem extrusion or the like. -It is also possible to form a sealing 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 using 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, the laminating adhesive layer formed by the 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 laminated material 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, 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, polypropylene, resin film or sheet such as ethylene-propylene copolymer, or polyvinyl alcohol having a barrier property against oxygen, water vapor, etc.
, A film or sheet of a resin such as saponified ethylene-vinyl acetate copolymer, and a colorant such as a pigment added to the resin, and other desired additives. Films or sheets of various colored resins 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 is usually about 5 μm to 300 μm, and more preferably about 10 μm.
m to 100 μm is desirable.

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-mentioned laminated material will be described. For example, when the packaging container is a soft packaging bag made of a plastic film or the like, Using a laminated material manufactured by such a method, the heat-sealing resin layer of the inner layer is made to face the surface, 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)
Can be manufactured, and in the present invention, a tube container or the like can also be manufactured using the above-mentioned laminated material. In the above, as a method of heat sealing, for example, a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high-frequency seal, an ultrasonic seal
Can be performed by a known method such as In the present invention, a spout such as a one-piece type, a two-piece type, or the like, or a zipper for opening and closing can be arbitrarily attached to the packaging container as described above.

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

[0034]

EXAMPLES The present invention will be described more specifically with reference to examples. Example 1 First, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane was used as a silane coupling agent, and 1.0% by weight of the silane coupling agent, 1.0% by weight of silica powder, and polyurethane 13-15% by weight of resin
Nitrocellulose 3-4% by weight, toluene 31-38% by weight, methyl ethyl ketone (MEK) 29-30% by weight, isopropyl alcohol (IPA) 15-16%
Was prepared. On the other hand,
On one surface of a biaxially stretched nylon 6 film having a thickness of 15 μm, a thickness of 200 μm was formed using chemical vapor deposition (CVD).
Å was formed by stacking two layers of a silicon oxide deposition film. next,
Using the above polyurethane resin composition,
Two layers of the deposited silicon oxide film having a thickness of 200 ° formed as described above are coated on the surface of the deposited silicon oxide film by using a roll coating method. After drying for 2 seconds, a coating thin film (thickness: 1.0 g / m ² , dry state) of the polyurethane resin composition was formed. 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 coating thin film surface of the polyurethane resin composition formed as described above. Using an adhesive for laminating, this is coated by a gravure roll coating method to a film thickness of 1 μm to form an adhesive layer for laminating. On the surface of the adhesive layer, a linear low-density polyethylene and an ethylene-α-olefin copolymer polymerized using a metallocene catalyst are used, each of which is coextruded to a thickness of 30 μm and coextruded to a thickness of 60 μm. A heat-sealing resin layer composed of an extruded film was formed, and a laminate according to the present invention having the following layer constitution was produced. 15 μm thick biaxially stretched nylon 6 film, thickness 20
2 layers of vapor-deposited silicon oxide of 0 ° / coating thin film of polyurethane resin composition / adhesive layer for lamination of 1 μm thickness / heat-sealing resin layer of 60 μm thickness 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 2 First, γ-glycidoxypropyltrimethoxysilane was used as a silane coupling agent, and 1.0% by weight of the silane coupling agent, 1.0% by weight of silica powder, and polyurethane resin 13 -15% by weight, nitrocellulose 3
Polyurethane-based resin composition was prepared comprising ４4% by weight, 31-38% by weight of toluene, 29-30% by weight of methyl ethyl ketone (MEK), and 15-16% of isopropyl alcohol (IPA). On the other hand, on one surface of a biaxially stretched nylon 6 film having a thickness of 15 μm, two layers of vapor-deposited aluminum oxide having a thickness of 200 ° were formed using physical vapor deposition (PVD). Next, using the above-mentioned polyurethane-based resin composition, two layers of the above-formed aluminum oxide vapor-deposited film having a thickness of 200 ° were layered, and gravure coating was performed on the multilayered aluminum oxide-deposited film surface.
Using a coating method, coating is performed.
After drying at 20 ° C. for 20 seconds, a coating thin film of a polyurethane resin composition (thickness: 1.0 g / m ² , dry state)
Was formed. On the coated thin film surface of the polyurethane resin composition formed as described above,
A laminating adhesive consisting of a 7% ethyl acetate and toluene solution of a two-part curable polyurethane resin consisting of toluene and isocyanate is used.
A laminating adhesive layer is formed by coating to a film thickness of 1 μm by utilizing the coating method, and then a linear low density polyethylene and a metallocene catalyst are used on the laminating adhesive layer surface. And an ethylene-α-olefin copolymer polymerized and then co-extruded to a thickness of 30 μm to form a heat-sealing resin layer comprising a co-extruded film to a thickness of 60 μm. A laminated material according to the present invention having the following layer constitution was manufactured. 15 μm thick biaxially stretched nylon 6 film, thickness 20
2 layers of deposited aluminum oxide film of 0 ° / coating thin film of polyurethane resin composition / adhesive layer for lamination of 1 μm thickness / heat-sealing resin layer of 60 μm thickness 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 3 First, on one surface of a biaxially stretched nylon 6 film having a thickness of 15 μm, a two-layer film of deposited silicon oxide having a thickness of 150 ° was formed by chemical vapor deposition (CVD). Formed.
On the other hand, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane was used as a silane coupling agent, and 1.0% by weight of the silane coupling agent was added to water: 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 adjusted as described above, two layers of the silicon oxide deposited film having a thickness of 150 ° formed as described above were laminated, and the gravure coating was performed on the multilayered silicon oxide deposited film surface. Coating using a coating method, and then drying at 120 ° C. for 20 seconds, a coating thin film (0.5 g /
m ² , dry). Next, on a surface of the coating thin film formed as described above, a laminating adhesive composed of a 7% ethyl acetate and toluene solution of a two-part curable polyurethane resin composed of polyetherpolyol and isocyanate. Using a gravure roll coating method, this was coated to a film thickness of 1 μm to form an adhesive layer for laminating, and then on the adhesive layer for laminating,
A linear low-density polyethylene and an ethylene-α-olefin copolymer polymerized using a metallocene catalyst are used, each of which is co-extruded to a thickness of 30 μm to form a co-extruded film having a thickness of 60 μm. -A sealable resin layer was formed to produce a laminate according to the present invention having the following layer constitution. 15 μm thick biaxially stretched nylon 6 film, thickness 15
2 layers of vapor-deposited silicon oxide film of 0 ° / coating thin film of water / alcohol composition / adhesive layer for laminate of 1 μm thickness / heat-sealing resin layer of 60 μm thickness Using the produced laminated material, a three-sided seal-type plastic bag is manufactured by a die-roll filling and packaging machine, and at the same time, a liquid seasoning is filled. Thereafter, the opening is heat-sealed to fill and package. When the 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 4 First, a polyester resin composition containing a thermoplastic polyethylene terephthalate resin as a main component of a vehicle was prepared (solid content: 15%). On the other hand, on a biaxially stretched nylon 6 film having a thickness of 15 μm, a vapor-deposited silicon oxide film having a thickness of 200 ° is formed by chemical vapor deposition (CVD). A 200- [mu] m-thick aluminum oxide vapor-deposited film was formed on the vapor-deposited film by physical vapor deposition (PVD), and two vapor-deposited films were stacked.
Next, the above-prepared polyester resin composition was used on the surface of the deposited aluminum oxide film which was formed by laminating the above two layers, and this was coated using a gravure roll coating method. And then dried at 100 ° C. for 5 seconds,
A coated thin film (thickness: 1.0 g / m ² , dry state) was formed from the above polyester resin composition. 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. A low-density polyethylene and an ethylene-α-olefin copolymer polymerized using a metallocene catalyst are used, each of which is coextruded to a thickness of 30 μm and a coextruded film having a thickness of 60 μm. By forming a sealing resin layer, a laminated material according to the present invention having the following layer constitution was manufactured. 15 μm thick biaxially stretched nylon 6 film, thickness 20
2 layers of deposited film of silicon oxide of 0 ° and deposited film of aluminum oxide of 200 ° thickness / coating thin film by polyester resin composition / laminate adhesive layer of 1 μm thickness / heater of 60 μm thickness Tosile Resin Layer Using the laminated material produced above, a three-sided seal-type plastic bag is produced by a die-roll filling and packaging machine, and a liquid seasoning is filled. When the packaged product was produced by tosealing, it had a high barrier property, no deterioration of the barrier property was recognized, and a very good result having excellent laminate strength was obtained.

Example 5 First, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane was used as a silane coupling agent, and 1.0% by weight of the silane coupling agent and 1.0% by weight of silica powder were used. %, 13-15% by weight of polyurethane resin,
Nitrocellulose 3-4% by weight, toluene 31-38% by weight, methyl ethyl ketone (MEK) 29-30% by weight, isopropyl alcohol (IPA) 15-16%
Was prepared. On the other hand,
One side of a biaxially stretched nylon 6 film having a thickness of 15 μm is formed on a surface of 200 mm thick by chemical vapor deposition (CVD).
Of silicon oxide deposited in two layers. Next, using the above-mentioned polyurethane-based resin composition, a roll coat method was applied to the surface of a 200-mm-thick silicon oxide vapor-deposited film obtained by laminating the two-layer vapor-deposited film formed above. Then, the coating was dried at 100 ° C. for 5 seconds to form a coating thin film (thickness: 0.4 g / m ² , dry state) of the above-mentioned 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 coating thin film surface of the polyurethane resin composition formed as described above. Using an adhesive for laminating, this is coated by a gravure roll coating method to a film thickness of 1 μm to form an adhesive layer for laminating. On the surface of the adhesive layer, a linear low-density polyethylene and an ethylene-α-olefin copolymer polymerized using a metallocene catalyst are used, each of which is coextruded to a thickness of 30 μm and coextruded to a thickness of 60 μm. A heat-sealing resin layer composed of an extruded film was formed, and a laminate according to the present invention having the following layer constitution was produced. 15 μm thick biaxially stretched nylon 6 film, thickness 20
2 layers of deposited silicon oxide film of 0 ° / coating thin film of polyurethane resin composition / laminate adhesive layer of 1 μm thickness / heat-sealing resin layer of 60 μm thickness Using a laminated material, a three-sided seal-type plastic bag is manufactured by a die-roll filling and packaging machine, and at the same time, a liquid seasoning is filled. Thereafter, the opening is heat-sealed to fill the packed product. As a result of the production, 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, γ-glycidoxypropyltrimethoxysilane was used as a silane coupling agent, and 1.0% by weight of the silane coupling agent, 1.0% by weight of silica powder, and polyurethane resin 13 -15% by weight, nitrocellulose 3
Polyurethane-based resin composition was prepared comprising ４4% by weight, 31-38% by weight of toluene, 29-30% by weight of methyl ethyl ketone (MEK), and 15-16% of isopropyl alcohol (IPA). On the other hand, a vapor-deposited film of aluminum oxide having a thickness of 200 ° is formed on one surface of a biaxially stretched nylon 66 film having a thickness of 15 μm by physical vapor deposition (PVD). On the vapor-deposited film, a thickness of 20
A 0 ° silicon oxide vapor deposition film was formed, and two layers of vapor deposition films were layered. Next, using the above-mentioned polyurethane-based resin composition, a gravure coating was performed on the surface of a 200-mm-thick silicon oxide vapor-deposited film obtained by laminating the two-layer vapor-deposited films formed above.
Using a coating method, coating is performed.
After drying at 20 ° C. for 20 seconds, a coated thin film of a polyurethane resin composition (thickness: 0.3 g / m ² , dry state)
Was formed. On the coated thin film surface of the polyurethane resin composition formed as described above,
A laminating adhesive consisting of a 7% ethyl acetate and toluene solution of a two-part curable polyurethane resin consisting of toluene and isocyanate is used.
A laminating adhesive layer is formed by coating to a film thickness of 1 μm by utilizing the coating method, and then a linear low density polyethylene and a metallocene catalyst are used on the laminating adhesive layer surface. And an ethylene-α-olefin copolymer polymerized and then co-extruded to a thickness of 30 μm to form a heat-sealing resin layer comprising a co-extruded film to a thickness of 60 μm. A laminated material according to the present invention having the following layer constitution was manufactured. 15 μm thick biaxially stretched nylon 66 film, thickness 2
00Å aluminum oxide film / 200Å silicon oxide film / polyurethane resin composition
Thinning film / Laminate adhesive layer with a thickness of 1 μm / heat-sealing resin layer with a thickness of 60 μm Using the laminated material produced above, a three-side seal type is formed using a die-roll filling and packaging machine. A plastic bag was produced and filled with a liquid seasoning. After that, the opening was heat-sealed to produce a filled and packaged product. And excellent results with excellent laminating strength were obtained.

COMPARATIVE EXAMPLE 1 A thickness of 20 formed by chemical vapor deposition (CVD)
A biaxially stretched nylon 6 film having a thickness of 15 μm and a silicon oxide film having a thickness of 200 μm having a vapor deposition film of silicon oxide having a thickness of 0 ° was coated with 7% of the same two-component curable polyurethane resin as in Example 1 above. A laminating adhesive consisting of a solution of ethyl acetate and toluene was used, and this was gravure roll-coated.
Using a coating method, a film is coated to a film thickness of 1 μm and laminated.
A low-density polyethylene and an ethylene-α-olefin copolymer polymerized using a metallocene catalyst are used on the surface of the laminating adhesive layer. Were coextruded to a thickness of 30 μm to form a heat-sealing resin layer made of a coextruded film to a thickness of 60 μm, thereby producing a laminated material having the following layer constitution. 15 μm thick biaxially stretched nylon 6 film, thickness 20
0 ° deposited silicon oxide film / Laminate adhesive layer having a thickness of 1 μm / heat-sealing resin layer having a thickness of 60 μm Using the laminated material produced above, a three-sided die roll packing machine is used. A seal-type plastic bag was produced, and a liquid seasoning was filled. Thereafter, the opening was heat-sealed to produce a filled packaging product.

COMPARATIVE EXAMPLE 2 A thickness of 20 formed by 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 made of a co-extruded film to a thickness of 60 μm, thereby producing a laminated material having the following layer constitution. 15 μm thick biaxially stretched nylon 6 film, thickness 20
0 ° deposited aluminum oxide film / Laminate adhesive layer having a thickness of 1 μm / heat-sealing resin layer having a thickness of 60 μm Using the laminated material produced above, a three-sided die-roll packing machine is used. A seal-type plastic bag was produced, and a liquid seasoning was filled. Thereafter, the opening was heat-sealed to produce a filled packaging product.

EXPERIMENTAL EXAMPLE 1 Each of the laminates produced in the above Examples 1 to 6 and a packaging container,
Each of the laminated materials and packaging containers manufactured in Comparative Examples 1 and 2 above was used. In Examples 1 to 6, the surface of the coating thin film and a low-density polyethylene layer or low-density polyethylene film having a thickness of 60 μm were used. And the comparative examples 1 and 2 were subjected to a laminating strength test and a tearing test between the surface of the deposited film having a thickness of 200 ° and the surface of the low-density polyethylene layer or film having a thickness of 60 μm. . The laminating strength test was performed using a peel tester (Orientec Co., Ltd., model name, Tensilon universal tester), sample 15 mm wide, peel angle 90 °, load cell 5k
gf 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.

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

Experimental Example 2 Further, the laminated materials produced in Examples 1 to 6 and the laminated materials produced in Comparative Examples 1 to 2 were produced by bag making or box making using these materials. For packaging containers,
The following data was measured. (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.

(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 excellent in oxygen permeability and water vapor permeability, while those of Comparative Examples 1 to 4 were excellent.
Both of the two were inferior.

EXPERIMENTAL EXAMPLE 3 Further, the laminated materials produced in Examples 1 to 6 and the laminated materials produced in Comparative Examples 1 and 2 were used to make a bag or a box to form a small bag. The following data was measured for the small bag packaging container. (1). Measurement of sensory evaluation This was carried out by filling the small pouch packaging container prepared above with 10 cc of dressing (blue diso dressing), placing 250 sealed bags in an aluminum foil laminated pouch, and sealing the bag. After storage at 2 ° C. for 2 days, the aluminum foil laminated pouch was opened, and sensory evaluation was performed by five panelists. The results are shown in Table 3 below.

(Table 3) The sensory evaluation points in Table 3 above were almost odorless,
The evaluation was made based on 1 point, a little odor, 3 points, quite odor, and a total score of 5 persons as a sensory evaluation score.

As is clear from the results shown in Table 3 above, those of Examples 1 to 6 are excellent in fragrance retention and have good storage suitability, whereas those of Comparative Examples 1 and 2 are It was inferior in fragrance retention and lacked in storage suitability.

[0051]

As is clear from the above description, the present invention provides a nylon film having excellent toughness such as impact resistance and piercing resistance, a multilayer of inorganic oxide thin films, organic and inorganic properties. Focusing on a silane coupling agent having, a polyurethane-based resin having an extensibility, a polyester-based resin, and the like, first, on one surface of the nylon film, at least two or more inorganic oxide thin films are laminated to form a multilayer. A coating thin film of a primer composition or a polyester resin composition containing a silane coupling agent is provided on the inorganic oxide thin film;
At least a heat-sealing resin layer is formed on the surface of the thin film via a laminating adhesive layer formed by a curing reaction between the polyester polyol or polyether polyol and isocyanate. Laminating to produce a laminated material, and then using the laminated material to make a bag or box to produce a packaging container, then, the contents in the packaging container,
In particular, it is packed with liquid or viscous contents such as liquid seasonings, and has excellent transparency, high barrier properties against oxygen gas or water vapor, etc., as well as impact resistance, puncture resistance, and laminating properties. -Excellent strength, etc., suitability for filling and packaging liquid or viscous contents, no cracks during post-processing, extremely high post-processing suitability, A transparent barrier film having sufficient microwave oven suitability and various packaging materials, particularly liquid or viscous contents, a laminate material and a packaging container using the same. Etc. can be manufactured.

[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 Inorganic oxide thin film 3 Coating thin film 4 Heat-sealing resin layer 5 Anchor-coating agent layer 5a Laminate adhesive layer 6 Seal part A Laminating material B Laminating material C Three-way seal type flexible packaging container D Two-way seal type flexible packaging container

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08J 5/18 CFG C08J 5/18 CFG C09J 175/04 C09J 175/04 C23C 14/08 C23C 14/08 A 14/10 14/10 // C08L 77:10 (72) Inventor Mitsunori Tsuzuki 1-1-1, Ichigaya Kagacho, Shinjuku-ku, Tokyo Inside Dai Nippon Printing Co., Ltd. (72) Hideaki Takahashi Ichigaya, Shinjuku-ku, Tokyo 1-1-1 Kagacho Dai Nippon Printing Co., Ltd. (72) Inventor Hiroshi Yamamoto 1-1-1 Ichigaya Kagamachi, Shinjuku-ku, Tokyo F-term in Dai Nippon Printing Co., Ltd. 3E086 AD01 AD02 BA04 BA15 BA24 BA40 BB01 BB22 BB31 BB51 CA01 CA11 CA28 4F071 AA54 AF07 AF23 AH04 BA01 BB08 BC01 4F100 AA01H AA17B AA17C AA19B AA20B AH06D AH10D AJ06 AK01E AK41D AK41G AK41AK5K AK46A 1J AK51K AK52D AK54G AK54J AK54K AK62 AK63 AL01G AL05D BA05 BA07 CA23D CB00 DA01 EH66B EH66C EJ38A EJ61D EJ67D GB16 JC00 JD03 JD04 JK02G JK06 JK08G JK10 JL01 JL11 JL12E JM02B JM02C JN01 YY00G 4J040 EF111 EF131 LA06 NA06 NA08 4K029 AA11 AA25 BA44 BA46 BB02 GA03

Claims (12)

[Claims] At least one inorganic oxide thin film is provided on one side of a nylon film in a form of a multilayer structure, and a primer composition containing a silane coupling agent is further provided on the inorganic oxide thin film. A laminate comprising a coating thin film made of a product or a polyester-based resin composition, and further having at least a heat-sealing resin layer laminated on the coating thin film. 2. The laminated material according to claim 1, wherein the nylon film is a biaxially stretched nylon film. 3. The laminated material according to claim 1, wherein the inorganic oxide thin film comprises an inorganic oxide vapor-deposited film. 4. The laminated material according to claim 1, wherein the deposited film of the inorganic oxide comprises a deposited film of silicon oxide or aluminum oxide. 5. The laminate according to claim 1, wherein the inorganic oxide thin film is formed by depositing an inorganic oxide by a physical vapor deposition method. 6. The laminated material according to claim 1, wherein the inorganic oxide thin film comprises a vapor deposited inorganic oxide film formed by a chemical vapor deposition method. 7. The laminate according to claim 1, wherein the primer composition comprises a polyurethane resin composition containing a silane coupling agent and a filler. 8. The laminate according to claim 1, wherein the primer composition comprises a water / alcohol-based composition containing a silane coupling agent. 9. A laminate comprising an anchor coat layer or a laminating adhesive layer interposed between a coating thin film and a heat-sealing resin layer. The laminate according to any one of claims 1 to 8, wherein 10. The laminating adhesive layer is formed of 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 9 characterized by the above-mentioned. 11. 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 10, wherein the laminate has a tensile elongation of 300% to 550% as measured under the following conditions. 12. A nylon composition comprising at least two layers of an inorganic oxide thin film on one surface of a nylon film, and a primer composition or a polyester containing a silane coupling agent on the inorganic oxide thin film. A coating thin film made of a base resin composition is provided, and a laminated material obtained by laminating at least a heat-sealing resin layer on the coating thin film is used. A packaging container comprising: