JP2001047546A - Laminated material and packaging container using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance transparency, barrier properties, impact resistance, laminat ing strength or the like, by providing a membrane of inorg. oxide, a coating membrane of a polyurethane resin compsn. and a printing pattern layer on the surface of a flexible plastic substrate successively, and providing a heat- sealable resin layer on the entire surface of the printing pattern layer. SOLUTION: A membrane 2 of inorg. oxide is provided on one surface of a flexible plastic substrate 1, and a coating membrane 3 comprising a polyurethane resin cimpsn. containing a silane coupling agent and a filter is provided thereon. Further, a printing pattern layer 4 comprising an ink compsn. based on a polyurethane resin and vehicle is provided on the surface of the membrane 3, and a heat-sealable resin layer 6 is laminated on the entire surface through an one to two-pack type curable polyurethane laminating adhesive layer 5. As the silane coupling agent, binary reactive organofunctional silane monomers can be used and, and the filler, for example, calcium carbonate, barium sulfate, alumina white, silica, talc and the others are designated.

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 and transparency.
Various products in the non-food fields such as food packaging, pharmaceutical packaging, detergents, shampoos, oils, toothpastes, etc., having excellent barrier properties against water vapor or oxygen gas, impact resistance, etc., and good storage suitability. Filling and packaging suitability,
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 and water vapor 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 configuration 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. These are excellent in transparency, and have a high barrier property and aroma retaining property against water vapor, oxygen, and the like, as compared with a laminate material for packaging using a conventional aluminum foil or the like. No environmental problems at the time of disposal, packaging materials,
In addition, the demand is greatly expected.

[0003]

However, the barrier performance of the above-mentioned transparent barrier film, a laminate material for packaging using the same, and the like, is higher than that of a conventional barrier material such as an aluminum foil. There is a problem that performance is inferior. For this reason, in the above-mentioned transparent barrier film, a laminated material for packaging using the same, in order to improve the barrier performance, the thickness of the vapor-deposited film is increased, or a layer of the entire laminated body including the barrier layer is formed. For example, attempts have been made to increase the thickness of the film. 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. Even more, in the above-mentioned transparent barrier film, and packaging laminates 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 the same problems as described above are likely to occur. 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,
This has the same problem as described above. In addition, when the above film thickness is improved, the deposited film is colored, and, for example, when used as a packaging material, there is a problem that the commercial value of the contents is impaired. Furthermore, in the case of producing a laminated material for packaging by extruding a film or sheet of another resin on the transparent barrier film as described above, or performing a coating process or a dry laminating process,
There is also a problem that the adhesive strength between the transparent barrier film and the laminating adhesive, the anchor coating agent, etc. is low, and the laminating strength is poor, and often causes delamination or the like in the laminated material. There is a problem. In particular, when an organic silicon compound or the like is used as a vapor deposition monomer and a silicon oxide vapor deposition film is formed by a chemical vapor deposition method or the like, the vapor deposition film contains an organic silicon component and the like. Is poor, for example, even if a printed pattern layer or an adhesive layer for laminating is formed on the surface of the vapor-deposited film, the tight adhesion is poor and often shows a phenomenon such as delamination. It is extremely difficult to produce a desirable laminate. Thus, in the above, in order to improve the adhesive force with the printed pattern layer or the adhesive layer, plasma treatment,
In some cases, pretreatment such as corona treatment is performed, but the effect is hardly recognized in the transparent barrier film. Therefore, the present invention has been made in view of the above situation,
It has excellent transparency and high barrier properties, and is also rich in impact resistance and has suitability for post-processing. Furthermore, it has excellent laminate strength, has laminate suitability, and fills the contents. An object of the present invention is to provide a transparent barrier film having good packaging suitability, a laminated material and a packaging container using the same.

[0004]

The present inventors have conducted various studies to solve the above-mentioned problems, and as a result, have found that a silane coupling agent having organic and inorganic properties and a polyurethane-based resin having extensibility have been obtained. First, a thin film of an inorganic oxide is provided on one surface of a flexible plastic substrate, and a polyurethane-based material containing a silane coupling agent and a filler is further provided on the thin film of the inorganic oxide. After providing a coating thin film of a resin composition, and further providing a desired print pattern layer of an ink composition containing a polyurethane resin as a main component of the vehicle on the surface of the coating thin film, the print pattern layer is formed. On the entire surface including a one- or two-part curable polyurethane-based laminating adhesive layer formed by a curing reaction between polyester polyol or polyether polyol and isocyanate, At least, a laminated material is manufactured by laminating the heat-sealing resin layer, and then a packaging container is manufactured using the laminated material to form a bag or a box, and the packaging container is manufactured. When filled with various articles, it has excellent transparency and high barrier properties against oxygen gas or water vapor, and also has excellent impact resistance, laminate strength, etc., and is suitable for filling and packaging of contents. And has no post-processing cracks and the like, and has extremely high post-processing suitability.Furthermore, even if the packaged product is subjected to microwave oven, it has sufficient microwave oven suitability and various packaging materials The present invention has been completed by finding that a laminated material having packaging suitability for an article and a packaging container and the like using the same 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 silane coupling agent and a filler are further provided on the thin film of the inorganic oxide. A coating thin film made of a polyurethane resin composition containing the same, a printing pattern layer is further provided on the coating thin film, and the entire surface including the printing pattern layer is coated with an adhesive layer via an adhesive layer. The present invention relates to a laminated material provided with a sealable resin layer and a packaging container using the same.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. First, the configuration of the laminated material according to the present invention and the configuration of a packaging container using the same will be described with reference to the drawings by exemplifying a few examples. FIG. 1 is a schematic diagram showing the layer configuration of the laminated material according to the present invention. FIG. 2, FIG. 3, FIG. 4, FIG. 5, and FIG. 6 are plan views showing the configuration of a packaging container made from a bag or a box using the laminated material according to the present invention. It is a perspective view.

First, a laminated material A according to the present invention, as shown in FIG.
A thin film 2 of an inorganic oxide is provided by a chemical vapor deposition method or a physical vapor deposition method, and a polyurethane resin composition containing a silane coupling agent and a filler on the thin film 2 of the inorganic oxide. After a coating thin film 3 made of a material is provided, and a desired print pattern layer 4 made of an ink composition containing a polyurethane resin as a main component of a vehicle is further provided on the surface of the coating thin film 3, and then the printing is performed. A one- or two-part curable polyurethane-based laminating adhesive layer 5 formed on the entire surface including the pattern layer 4 by a curing reaction between the polyester polyol or polyetherpolyol and the isocyanate. In addition, at least the heat-sealing resin layer 6 is laminated. Thus, the above-described examples are merely examples of the laminate according to the present invention, and are not limited thereto.
Although not shown, in addition to the flexible plastic base material, the heat-sealing resin layer, etc., other base materials may be used depending on the purpose of use, the contents to be filled and packed, the distribution channel, the sales form, the use, and the like. Can be arbitrarily laminated to design and manufacture various forms of laminated materials.

Next, in the present invention, the structure of the packaging container according to the present invention, which is formed by using the above-mentioned laminated material to form a bag or a box, will be described. By way of example, a description will be given of a packaging container made from a bag or a box using the laminated material A shown in FIG. 1, as shown in a schematic perspective view of FIG. Prepared, and the heatsink located on the innermost layer
The surfaces of the conductive resin layers 6 and 6 are superimposed on each other, and thereafter, three sides of the outer peripheral edge are heat-sealed to seal them.
By forming the sealing parts 7, 7, 7, the three-way seal type flexible packaging container B according to the present invention can be manufactured. Thus,
In the above-mentioned three-way seal type flexible packaging container B, the contents can be filled from the upper opening, and then the opening can be heat-sealed to produce a packaged product. .

Next, as a packaging container according to the present invention, as shown in a schematic plan view of FIG. 3, for example, the laminated material A shown in FIG. 1 is used.
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. 1 (indicated by a dotted line), a blank plate 9 for forming a paper container having a sticking portion 8 and the like.
Then, as shown in the schematic perspective view of FIG. 4, the sticking portion 8 of the blank plate 9 is overlapped with the other side end portion 10 (shown in FIG. 3), and the The superposed portion is heat-sealed to form the side end seal portion 11 to produce the body portion 12, and the lower portion of the body portion 12 is folded in a conventional manner to be heat-sealed. The bottom portion 13 is formed, and the upper portion thereof is heat-sealed in accordance with a conventional method to form the roof type seal portion 14, thereby manufacturing the roof type paper packaging container C according to the present invention. can do.

Further, as the packaging container according to the present invention, as shown in the schematic plan view of FIG. 5, for example, the laminated material A shown in FIG. 1 is used.
Although not shown, a paper base is further laminated on the flexible plastic base constituting the laminated material A, and a heat-sealing resin layer is further formed on the paper base. Forming and manufacturing a laminated material, using the laminated material, and then punching out a rectangular paper container forming blank plate 9a having a sticking portion 8a and the like and capable of forming a cylindrical body. Then, as shown in the schematic perspective view of FIG.
a is overlapped with the other side end 10a (shown in FIG. 5),
The overlapped portion is heat-sealed to form a side end seal portion 11a to produce a cylindrical body portion 12a.
In the lower portion of 2a, for example, a bottom plate 15 is formed by heat sealing a cylindrical bottom plate 15 to form a bottom seal portion 16, and further in the upper portion of the cylindrical container 12a, for example. ,
Heat sealing a cylindrical lid plate 19 having a drinking opening 18 sealed with a peeling off piece 17 to form an upper seal portion 20
Is formed to form the lid 19a, and the cylindrical paper can-shaped packaging container D according to the present invention can be manufactured. In the present invention, it is needless to say that the present invention is not limited to the above-illustrated packaging container, and that various types of packaging containers can be manufactured depending on the purpose, application, and the like. Needless to say.

[0011] Next, in the present invention, the materials and manufacturing method of the laminated material according to the present invention and the packaging container and the like using the same will be described. Various materials, manufacturing methods and the like can be adopted. First, in the present invention, the material constituting the laminated material according to the present invention will be described. First, as a flexible plastic substrate, it withstands the conditions for forming a thin film of an inorganic oxide, etc. Any plastic film or sheet can be used as long as it is firmly and tightly adhered to the film and can hold it satisfactorily. Specifically, for example, polyolefin resins such as polyethylene, polypropylene, and polybutene;
Acrylic resin, polyvinyl chloride resin, polystyrene resin, polyvinylidene chloride resin, saponified ethylene-vinyl acetate copolymer, polyvinyl alcohol resin, polycarbonate resin, fluorine resin, Films or sheets of various resins such as polyvinyl acetate resin, acetal resin, polyester resin, polyamide resin and others can be used. These resin films or sheets may be uniaxially or biaxially stretched, and may have a thickness of 1
About 0 to 200 μm, preferably about 10 to 100 μm is desirable. If necessary, the film or sheet of the above resin may be coated with an anchor coating agent or the like and subjected to a surface smoothing treatment or the like.
Further, a pretreatment such as a plasma treatment or a corona treatment can be optionally performed.

Further, in the present invention, as the inorganic oxide thin film constituting the laminate according to the present invention, basically any thin film obtained by making a metal oxide 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 for 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, a 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 Or, using a metal or metal oxide as a raw material, oxidizing by introducing oxygen and depositing on a flexible plastic substrate, an oxidation reaction deposition method, and a plasma-assisted type method for further assisting the oxidation reaction with plasma. A deposition film can be formed by an oxidation reaction deposition method or the like. Also,
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, a specific example of a method of forming a thin film of an inorganic oxide is shown in FIG. 7. FIG. 7 is a schematic configuration diagram showing an example of a roll-up type vacuum evaporator. As shown in FIG. 7, the flexible plastic substrate 1 is unwound from an unwinding roll 33 in a vacuum chamber 32 constituting a winding type vacuum evaporator 31. Next, the flexible plastic substrate 1 unwound from the unwinding roll 33 as described above.
Passes through the coating drum 34 and passes through the deposition chamber-3.
5 is introduced. Thus, in the evaporation chamber 35, the evaporation source (for example, aluminum or aluminum oxide) heated in the crucible 36 is evaporated,
Further, if necessary, while blowing oxygen gas or the like from the oxygen outlet 37, one of the flexible plastic substrates 1 on the cooled coating drum 34 introduced into the vapor deposition chamber 35 described above. On the surface, a vapor-deposited film of an inorganic oxide is formed through the masks 38, 38, and then the flexible plastic substrate 1 on which the vapor-deposited film of the inorganic oxide is formed is fed into the vacuum chamber 32, and further, Take-up roll 3
By winding it around 9, a flexible plastic substrate having a thin film of the inorganic oxide according to the present invention can be manufactured.

Further, in the present invention, a specific example of the above-described plasma chemical vapor deposition method is illustrated. FIG. 8 is a schematic configuration diagram illustrating an example of a plasma chemical vapor deposition apparatus. As shown in FIG. 8, an unwinding roll arranged in a vacuum chamber 42 constituting the plasma chemical vapor deposition apparatus 41.
The flexible plastic substrate 1 is fed from the roll 43 via the auxiliary roll 44 at a constant speed, and is conveyed onto the peripheral surface of the cooling / electrode drum 45. Next, the flexible plastic substrate 1 is conveyed onto the peripheral surface of the cooling / electrode drum 45, and is supplied from the raw material volatilizing supply devices 46, 47, and 48, for example, an organic silicon compound, oxygen gas, and inert gas. A mixed gas composed of a gas or the like is introduced into the vacuum chamber 42 through the material supply nozzle 49, and the thin film of an inorganic oxide such as a silicon oxide vapor-deposited film is formed by the glow discharge plasma 50 on the flexible film. It is formed on one surface of the conductive plastic substrate 1 to form a film. At this time, a predetermined voltage is applied to the cooling / electrode drum 45 from a power supply 51 disposed outside the vacuum chamber 42, and a magnet 52 is provided near the cooling / electrode drum 45. This arrangement promotes the generation of plasma and prepares a thin film of an inorganic oxide such as a deposited film of silicon oxide. Next, the flexible plastic substrate 1 on which a thin film of an inorganic oxide such as a silicon oxide vapor-deposited film is formed is wound around a winding roll 53 via an auxiliary roll 44, and the present invention is applied. Thus, a flexible plastic substrate having the inorganic oxide thin film can be manufactured. In the figure, 53 represents a vacuum pump.

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 having 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 100 to 500 °. Thus, in the present invention, as the silicon oxide thin film as described above,
A vapor-deposited film formed using 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 organic silicon compounds as described above, 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 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.

Further, in the present invention, the silane coupling agent for forming a coating thin film of a polyurethane resin composition containing a silane coupling agent and a filler constituting the laminate according to the present invention includes: Binary reactive organofunctional silane monomers can be used, for example, γ-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris (β-methoxyethoxy) silane,
γ-methacryloxypropyltrimethoxysilane, β
-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, N-β (aminoethyl)-
γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane, γ- One or more of aqueous solutions of aminopropylsilicone and the like can be used. In the silane coupling agent as described above, a functional group at one end of the molecule, usually, a chloro, alkoxy, or acetoxy group, or the like is hydrolyzed to form a silanol group (SiOH). The metal constituting the thin film of the substance, or an active group on the surface of the thin film of the inorganic oxide, for example, a functional group such as a hydroxyl group, by some action, for example, causes a reaction such as a dehydration condensation reaction, and the inorganic oxide thin film 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 adhesive layer for coating, anchor coating agent layer, other layers, etc. to form a strong bond, and further, the above-mentioned printed pattern layer, adhesive layer for laminating, The heat-sealing resin layer is firmly and tightly adhered through the anchor coating agent layer and the like, and the laminating layer is formed.
Thus, in the present invention, a strong laminated structure having high laminate strength can be formed. In the present invention, the inorganic and organic properties of the silane coupling agent are utilized, and the heat transfer is performed via the inorganic oxide thin film and the printing pattern layer, the adhesive layer or the anchor coating agent layer. To improve the tight adhesion with the resin layer, thereby increasing the laminate strength and the like.

Next, in the present invention, as a filler for forming a coating thin film of a polyurethane resin composition containing a silane coupling agent and a filler constituting the laminate according to the present invention, for example, carbonic acid Calcium, barium sulfate, alumina white, silica, talc, glass frit, resin powder, and the like can be used. The above-mentioned filler adjusts the viscosity and the like of the polyurethane-based resin composition liquid, improves its coating suitability, and binds to the polyurethane-based resin as a binder resin via a silane coupling agent. And to improve the cohesive force of the coating film.

Next, in the present invention, as a polyurethane resin forming a coating thin film of a polyurethane resin composition containing a silane coupling agent and a filler constituting the laminate according to the present invention, for example, Polyurethane resins obtained by reacting a polyfunctional isocyanate with a hydroxyl group-containing compound can be used. Specifically, for example, tolylene diisocyanate,
Aromatic polyisocyanates such as diphenylmethane diisocyanate and polymethylene polyphenylene polyisocyanate, or hexamethylene diisocyanate;
By reacting a polyfunctional isocyanate such as an aliphatic polyisocyanate such as xylylene diisocyanate with a hydroxyl group-containing compound such as polyether polyol, polyester polyol, polyacrylate polyol, or the like. The obtained one-pack or two-pack curable polyurethane 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,
The purpose of the present invention is to improve the suitability for post-processing such as laminating or bag-making, and to prevent the occurrence of cracks in the inorganic oxide thin film during post-processing.

In the present invention, the polyurethane resin composition is used in an amount of 0.05 to 10% by weight of the silane coupling agent based on 1 to 30% by weight of the polyurethane resin.
%, Preferably 0.1% to 5% by weight, filler 0.1% to 20% by weight, preferably 1% to 10% by weight, and if necessary, stabilizer , Curing agent,
Additives such as a crosslinking agent, a lubricant, an ultraviolet absorber and others are optionally added, and a solvent, a diluent and the like are added and mixed well to prepare a polyurethane resin composition. Thus, in the present invention, the above-mentioned polyurethane-based resin composition may be used, for example, by roll coating, gravure coating, knife coating, or the like.
The present invention comprises coating the inorganic oxide thin film with a dip coat, spray coat or other coating method and then drying the coated film to remove the solvent, diluent and the like. Thus, a coating thin film can be formed. In the present invention, the thickness of the coating thin film of the polyurethane resin composition, for example,
It is preferably about 0.01 to 50 μm, and more preferably about 0.1 to 5 μm.

Next, in the present invention, the printed pattern layer constituting the laminated material according to the present invention will be described. As the printed pattern layer, one or two or more of ordinary ink vehicles are used as main components. If necessary, plasticizer, stabilizer, antioxidant, light stabilizer, UV absorber,
Optionally, one or more additives such as a curing agent, a crosslinking agent, a lubricant, an antistatic agent, a filler, and the like,
Colorants such as dyes and pigments are added, and the ink composition is adjusted by sufficiently kneading with a solvent, a diluent, etc., and then using the ink composition, for example, gravure printing, offset printing, letterpress printing, Using a printing method such as screen printing, transfer printing, flexographic printing, etc., a desired printing pattern consisting of characters, figures, symbols, patterns, etc. is printed on the above-mentioned coating thin film, and the book is printed. The printed pattern layer according to the invention can be formed. Thus, in the present invention, the above-mentioned polyurethane-based resin is used as a main component of the vehicle as an ink vehicle, and if necessary, a plasticizer, a stabilizer, an antioxidant, a light stabilizer, UV absorber,
Optionally, one or more additives such as a curing agent, a crosslinking agent, a lubricant, an antistatic agent, a filler, and the like,
Colorants such as dyes and pigments are added, and the ink composition is adjusted by sufficiently kneading with a solvent, a diluent, etc., and then using the ink composition, for example, gravure printing, offset printing, letterpress printing, Using a printing method such as screen printing, transfer printing, flexographic printing, etc., a desired printing pattern consisting of characters, figures, symbols, patterns, etc. is printed on the above-mentioned coating thin film, and the book is printed. It is desirable to form a printed pattern layer according to the invention. In the present invention, as the ink vehicle, by using a polyurethane resin as described above, the reason is not clear, but as described above, the elongation of the thin film constituting the print pattern layer is improved, for example, It is intended to improve the suitability for post-processing such as laminating or bag-making, and to prevent the occurrence of cracks in the inorganic oxide thin film during post-processing.

Next, in the present invention, the adhesive layer constituting the laminate according to the present invention will be described. The adhesive layer is obtained by reacting the above-mentioned polyfunctional isocyanate with a hydroxyl group-containing compound. One- or two-component curable adhesive layers containing a polyurethane-based resin as a main component can be used. Specifically, for example, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, or hexamethylene diisocyanate, xylylene diisocyanate A polyfunctional isocyanate such as an aliphatic polyisocyanate such as a naphthalate; a polyether polyol; a polyester polyol;
1 to 2 obtained by reaction with a hydroxyl group-containing compound such as phenol, polyacrylate polyol, or the like.
An adhesive composition containing a liquid-curable polyurethane-based resin as a main component of a vehicle is used.
Coating, gravure coating, knife coating, dip coating, spray coating and other coating methods on the entire surface including the above-mentioned printed pattern layer, and then drying the solvent, diluent, etc. Thus, an adhesive layer constituting the laminate according to the present invention can be formed. In the above,
The thickness of the adhesive layer 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, similarly to the above, the elongation of the thin film constituting the adhesive layer is improved,
For example, it is intended to improve the suitability for post-processing such as laminating or bag-making, and to prevent the occurrence of cracks in the inorganic oxide thin film during the post-processing.

In the present invention, the adhesive layer constituting the laminate according to the present invention is JIS K
23 ° C, 50% RH with No. 4 dumbbell according to 6301
300 mm / min. 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 is synergistic with the above-mentioned coating thin film, printing pattern layer, etc., and the inorganic oxide thin film, coating thin film, printing pattern layer, Adhesive layer,
It is intended to improve the tight adhesion with the heat-sealing resin layer and the like, thereby preventing the occurrence of cracks and the like in the inorganic oxide thin film. In the above, the tensile elongation is 300
If it is less than 10%, it lacks flexibility, and cracks and the like are generated in the inorganic oxide thin film in laminating or post-processing such as bag making or box making, and the tensile elongation is 550%. If it exceeds, the flexibility is excessive and the tearing property is poor, and for example, the openability of the packaging container is poor, which is not preferable. 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, or an isocyanate-based anchor coating agent. 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, at the time of lamination, for example, polyurethane-based, polyester-based, polyamide-based, epoxy-based, poly (meth) acrylic, polyvinyl acetate-based, polyolefin-based or modified Various kinds of laminating such as solvent type, aqueous type, non-solvent type, or hot-melt type containing polyolefin, casein, wax, ethylene- (meth) acrylic acid copolymer, polybutadiene, etc. as the main components of the vehicle. Glue adhesives can be used. Thus, in the present invention, for example, roll coat, gravure coat, knife coat, dip coat,
An adhesive layer made of the adhesive for laminating according to the present invention can be formed by coating with a spray coat or another coating method and drying the solvent, diluent and the like. 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 heat-sealing resin forming the heat-sealing resin layer constituting the laminate according to the present invention can be melted by heat and fused to each other. Resin films or sheets 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 Polyolefin resin such as pentene polymer, polybutene polymer, polyethylene or polypropylene Acid-modified polyolefin resin modified with unsaturated carboxylic acids 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, in the present invention, a resin film or sheet as described above is used, and this is laminated via the above-mentioned adhesive layer by, for example, a dry laminating method or the like. It is capable of forming a sealable resin layer. Alternatively, in the present invention, the heat-sealing resin layer can also be formed by extrusion-coating and laminating the melt-extruded resin layer via the above-mentioned adhesive layer. In the present invention, heather
The thickness of the conductive resin layer is preferably about 5 μm to 300 μm, and more preferably about 10 μm to 100 μm.

Next, in the present invention, in the laminated material according to the present invention, in addition to the above materials,
For example, a resin film or sheet having strength, toughness, and heat resistance can be laminated, and specifically, for example, a polyester resin, a polyamide resin, a polyaramid resin, and a polyolefin. Films or sheets of a tough resin such as a base resin, a polycarbonate resin, a polystyrene resin, a polyacetal resin, a fluorine resin, and others 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 10 μm to 50 μm.
The m-th position is desirable. 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 base film, for example, various paper base materials 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.

Further, 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, etc. Polyethylene, polypropylene, film or sheet of resin such as ethylene-propylene copolymer, or, oxygen, polyvinylidene chloride having a barrier property against water vapor,
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 laminated. 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 150 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 may be 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-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)
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 the 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, various types of foods and drinks such as liquid beverages, confectioneries, powdery, liquid or solid seasonings, and other adhesives, adhesives and pressure-sensitive adhesives It is used for filling and packaging of various articles such as chemicals, detergents, cosmetics such as others, pharmaceuticals, miscellaneous goods such as chemical warmers, and others. 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, 0.3% by weight of the silane coupling agent, silica powder (particle diameter 2 μm). 0% by weight, polyurethane resin 1
A polyurethane resin composition comprising 5.6% by weight, 3.5% by weight of nitrocellulose, and 79.6% by weight of a mixed solvent of toluene, methyl ethyl ketone and isopropyl alcohol in a ratio of 4: 4: 2 was prepared. . Next, using the polyurethane resin composition adjusted as described above, a thickness of 200 Å previously formed by chemical vapor deposition (CVD) is used.
A 15 μm-thick biaxially stretched nylon film having a silicon oxide vapor-deposited film is coated by a gravure roll coating method on a 200 ° -thick silicon oxide vapor-deposited film, and then at 120 ° C. After drying for 20 seconds, a coating thin film (thickness 0.5 g / m ² , dry state) was formed from the above-mentioned polyurethane resin composition. Next, a desired printing pattern layer of four colors is formed on the coated thin film surface of the polyurethane resin composition formed above using a gravure printing method using an ink composition using a polyurethane resin as a vehicle. Is formed, an adhesive consisting of a 7% ethyl acetate solution of a two-pack curable polyurethane resin consisting of polyester polyol and isocyanate is used on the entire surface including the printed pattern layer, and this is gravure-coated. An adhesive layer (dry state) having a film thickness of 1 μm was formed by coating by a coating method, and low-density polyethylene was used on the surface of the adhesive layer formed above, and this was coated to a thickness of 60 μm.
m to give a laminated material according to the present invention having the following layer constitution. Biaxially stretched nylon film / silicon oxide vapor deposition film / coating thin film / printed pattern layer / adhesive layer / low density polyethylene layer 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 Using the polyurethane-based resin composition prepared in Example 1 above, the thickness formed by chemical vapor deposition (CVD) in the same manner as in Example 1 above. A biaxially stretched polyethylene terephthalate film having a thickness of 200 μm and having a thickness of 200 μm is coated on the surface of a 200 μm thickness silicon oxide deposition film using a gravure roll coating method. After drying at 120 ° C. for 20 seconds, a coating thin film (thickness: 1.0 g / m ² , dry state) of the polyurethane resin composition was formed. Next, on the coating thin film surface of the polyurethane resin composition produced above, using an ink composition having a polyurethane resin as a vehicle, by a gravure printing method,
After forming a desired print pattern layer of four colors, an adhesive consisting of a 7% solution of the same two-component curable polyurethane resin as in Example 1 above is used on the entire surface including the print pattern layer,
This was coated by a gravure roll coating method to form an adhesive layer (dry state) having a thickness of 1 μm, and then a low-density polyethylene film having a thickness of 60 μm was coated on the adhesive layer formed above. The laminate was laminated to produce a laminate according to the present invention. Further, a low-density polyethylene was used on the biaxially stretched polyethylene terephthalate film surface of the laminate produced above, and this was extruded to a thickness of 100 μm and laminated to produce a laminate having the following layer structure. did. Low-density polyethylene layer / bi-stretched polyethylene terephthalate film / deposited film of silicon oxide / coating thin film /
Printing Pattern Layer / Adhesive Layer / Low Density Polyethylene Film Using the laminated material produced above, first, the laminated material is rolled and the overlapped edge is heat-welded to form a tubular body for forming a tube. Then, a neck is formed at one end of the tubular body by injection molding using high-density polyethylene, and a cap is screwed onto the neck to form a tube.
The container was manufactured. Next, the contents are filled through the other opening of the tube container, and then the opening is sealed.
A tube-shaped packaged product was manufactured by sealing. The above product had a high degree of barrier properties and was suitable for filling and packaging the contents.

Example 3 Using the polyurethane-based resin composition prepared in Example 1 above, a thickness formed by chemical vapor deposition (CVD) in the same manner as in Example 1 above. A biaxially-stretched polypropylene film having a thickness of 200 μm and a silicon oxide film having a thickness of 200 ° is coated on the surface of the silicon oxide film having a thickness of 200 ° by using a gravure roll coating method. And dried for 20 seconds, and coated with a polyurethane resin composition (thickness: 1.
0 g / m ² , dry). Next, on the coated thin film surface of the polyurethane resin composition produced above, a desired printing pattern layer consisting of four colors is formed by a gravure printing method using an ink composition containing a polyurethane resin as a vehicle. Is formed, an adhesive consisting of a 7% solution of a two-component curable polyurethane resin as in Example 1 is used on the entire surface including the printed pattern layer, and this is coated by a gravure roll coating method. To form an adhesive layer (dry state) having a thickness of 1 μm, and then a low-density polyethylene film having a thickness of 60 μm is laminated on the surface of the adhesive layer formed as described above. A laminate according to the present invention was manufactured. Bi-stretched polypropylene film / silicon oxide vapor deposited film / coating thin film / printed pattern layer / adhesive layer / low density polyethylene film Using the laminated material produced above, make a bag with a bag making machine to form a three-way seal. Molded plastic bags were 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 4 First, γ-glycidoxypropyltrimethoxysilane was used as a silane coupling agent, and 0.3% by weight of the silane coupling agent, 1.0% by weight of silica powder, and 15% of a polyurethane resin 2.6% by weight, nitrocellulose
5 wt%, mixed solvent of toluene, methyl ethyl ketone and isopropyl alcohol in a ratio of 4: 4: 2
A polyurethane resin composition comprising 6% by weight was prepared. Using the polyurethane resin composition prepared above, a biaxially stretched polyethylene terephthalate having a thickness of 12 μm and having a deposited film of aluminum oxide having a thickness of 200 ° formed by physical vapor deposition (PVD). On the surface of the deposited film of aluminum oxide with a thickness of 200 mm
Coating was performed using a gravure roll coating method, followed by drying at 120 ° C. for 20 seconds to form a coated thin film (0.2 g / m ² dry state) of the polyurethane resin composition. Next, on the coated thin film surface of the polyurethane resin composition produced above, a desired printing pattern consisting of four colors was formed by a gravure printing method using an ink composition using a polyurethane resin as a vehicle. After the formation, an adhesive consisting of a 7% ethyl acetate solution of a two-pack curable polyurethane resin consisting of polyetherpolyol and isocyanate is used on the entire surface including the printed pattern layer, and this is gravure-coated. An adhesive layer (dry state) having a film thickness of 1 μm is formed by coating by a coating method, and then a low-density polyethylene is used on the surface of the adhesive layer.
This was extruded and coated to 80 μm to produce a laminated material having the following structure. Double-stretched polyethylene terephthalate film / aluminum oxide deposited film / coating thin film / printed pattern layer / adhesive layer layer / low density polyethylene layer A three-sided seal-type 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 5 Using the polyurethane resin composition prepared in Example 3 above, the thickness formed by physical vapor deposition (PVD) in the same manner as in Example 3 above. Using a gravure roll coating method, a biaxially stretched nylon film having a thickness of 200 μm and a biaxially stretched nylon film having a thickness of 200 μm is coated using a gravure roll coating method. And dry for 20 seconds
A coating thin film (thickness 0.5 g / m ² , dried) of the polyurethane resin composition was formed. After forming a desired printing pattern of four colors by a gravure printing method using an ink composition using a polyurethane-based resin as a vehicle, on a coating thin film surface of the polyurethane-based resin composition prepared above. An adhesive consisting of a 7% ethyl acetate solution of the same two-component curable polyurethane resin as in Example 3 was used on the entire surface including the printed pattern layer, and this was coated by a gravure roll coating method. Then, an adhesive layer (dry state) having a film thickness of 1 μm is formed, and then a low-density polyethylene film is laminated on the surface of the adhesive layer to a thickness of 60 μm. Was manufactured. Biaxially stretched nylon film / aluminum oxide deposited film / coating thin film / printed pattern layer / adhesive layer / low density polyethylene film. Using each of the laminated materials manufactured as described above, a three-side seal type plastic bag was manufactured 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, a 200 ° thick silicon oxide deposited film surface, and a gravure printing method using an ink composition containing a polyurethane resin as a vehicle. After forming a desired print pattern, an adhesive consisting of a 7% ethyl acetate solution of a two-component curable polyurethane resin as in Example 1 is used on the entire surface including the print pattern layer, and this is gravure coated. -An adhesive layer (dry state) having a film thickness of 1 µm is formed by a coating method, and 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. Biaxially stretched nylon film / silicon oxide deposited film / printed pattern layer / adhesive layer / low density polyethylene layer Using the laminated material produced above, make a bag with a bag making machine to form a three-way seal-type 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 packaging product.

COMPARATIVE EXAMPLE 2 A thickness of 20 formed by chemical vapor deposition (CVD)
Biaxially stretched polyethylene terephthalate film having a thickness of 12 μm and having a thickness of 0 ° deposited with silicon oxide having a thickness of 200 °
A printed pattern layer is formed on the surface of the silicon oxide vapor-deposited film in the same manner as in Example 1 described above, and the entire surface including the printed pattern layer is formed from a 7% ethyl acetate solution of a two-component curable polyurethane resin. Gravure roll-
An adhesive layer (dry state) having a thickness of 1 μm was formed by a coating method, and then a low-density polyethylene film having a thickness of 60 μm was laminated on the surface of the adhesive layer to produce a laminated material. Further, a low-density polyethylene was used on the biaxially stretched polyethylene terephthalate film surface of the laminate produced above, and this was extruded to a thickness of 100 μm and laminated to produce a laminate having the following layer structure. did. Low-density polyethylene layer / bi-stretched polyethylene terephthalate film / silicon oxide vapor deposition film / printed pattern layer / adhesive layer / low-density polyethylene film The overlapped edge 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 high-density polyethylene. Then, a cap is screwed onto the neck to make a tube.
The container was manufactured. Next, the contents are filled through the other opening of the tube container, and then the opening is sealed.
A tube-shaped packaged product was manufactured by sealing.

COMPARATIVE EXAMPLE 3 A thickness of 20 formed by physical vapor deposition (PVD)
12 μm thick with a deposited film of 0 ° aluminum oxide
On the surface of the biaxially stretched polyethylene terephthalate film of 200 mm thick aluminum oxide deposited film, a printed pattern layer was formed in the same manner as in Example 3 above, and further over the entire surface including the printed pattern layer. An adhesive consisting of a 7% ethyl acetate solution of a two-part curable polyurethane resin was used, and was coated by a gravure roll coating method to form a film having a thickness of 1%.
μm of an adhesive layer (in a dry state) is formed, and then a low-density polyethylene is used on the surface of the adhesive layer.
m, and a laminated material having the following layer constitution was manufactured. Bi-stretched polyethylene terephthalate film / aluminum oxide deposited film / printed pattern layer / adhesive layer / low density polyethylene layer Using the laminated material produced above, make a bag with a bag making machine to form a three-way seal type. 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 packaging product.

Comparative Example 4 Thickness of 20 Formed Using Physical Vapor Deposition (PVD)
15 μm thick with a deposited film of 0 ° aluminum oxide
A printed pattern layer was formed on the surface of the biaxially stretched nylon film having a thickness of 200 ° deposited with aluminum oxide in the same manner as in Example 3 above.
An adhesive consisting of a 7% ethyl acetate solution of a liquid-curable polyurethane resin is used and coated by a gravure roll coating method to form an adhesive layer (dry state) having a film thickness of 1 μm, Next, a 60 μm thick
Were laminated to produce a laminated material having the following layer constitution. Biaxially stretched nylon film / aluminum oxide vapor-deposited film / adhesive layer / low-density polyethylene film Using the laminated material produced as described above, a three-sided seal-type plastic bag was produced using 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 5 and the laminated materials manufactured in Comparative Examples 1 to 4 were used. Thin film surface and thickness 60 or 80μ
m low-density polyethylene layer or low-density polyethylene film, Comparative Examples 1 to 4 are a 200-mm-thick silicon oxide or 200-mm-thick aluminum oxide vapor-deposited film and a 60 or 80 μm-thick low-density polyethylene layer Alternatively, a lamination strength test and a tearing test with the surface of the low density polyethylene film were performed. The laminating strength test was performed using a peeling tester (Orientec Co., Ltd., model name, Tensilon universal testing machine), and the sample 1
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 addition, a tear test was performed by making a 10 mm cut in the end of the laminated material,
The test was performed at an angle of 180 degrees and a pulling speed of 3300 mm / min. The results are shown in Table 1 below.

[0044] In Table 1 above, when the tear resistance load is 300 g or less, it is judged that the tearing property is good.

As shown in the above Table 1, the laminates of Examples 1 to 5 have significantly higher laminating strength than those of Comparative Examples 1 to 4, indicating that the polyurethane containing a silane coupling agent was used. It has been found that the peel strength is improved by forming a coating thin film of the base resin composition. 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 5 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.

[0047] In Table 2 above, the unit of oxygen permeability is cm ³ / m
² / day, and the unit of water vapor permeability is g / day.
m ² / day.

As is clear from the results shown in Table 2 above, the oxygen permeability and the water vapor permeability of the laminated material were good in both the examples and the comparative examples, but were processed into packaging containers. Regarding the oxygen permeability and the water vapor permeability for the later ones, those of Examples 1 to 5 were good as they were in the oxygen permeability and the water vapor permeability, whereas those of Comparative Examples 1 to 4 were , All of which were inferior.

[0049]

As is apparent from the above description, the present invention focuses on an organic and inorganic silane coupling agent and an extensible polyurethane-based resin. On one surface of the material, a thin film of an inorganic oxide is provided, and further, on the thin film of the inorganic oxide, a coating thin film of a polyurethane-based resin composition containing a silane coupling agent and a filler is provided, Further, after a desired printed pattern layer made of an ink composition containing a polyurethane resin as a main component of the vehicle is provided on the surface of the coating thin film, a polyester polyol is coated on the entire surface including the printed pattern layer.
Through a one- or two-component curable polyurethane-based laminating adhesive layer formed by a curing reaction between the polyester or polyetherpolyol and the isocyanate,
The heat-sealing resin layer is laminated to produce a laminated material, and the laminated material is used to make a bag or a box to produce a packaging container. It has excellent transparency and high barrier properties against oxygen gas or water vapor, etc., and has excellent impact resistance, laminate strength, etc., and is suitable for filling and packaging of contents. In addition, there is no occurrence of cracks or the like during post-processing, and it has extremely high post-processing suitability.Furthermore, even if the packaged product is subjected to microwave oven, it has sufficient microwave suitability, and various articles as packaging materials can be used. A laminated material having suitability for packaging and a packaging container and the like using the same 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 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. 3 is a schematic perspective view showing a configuration of a packaging container formed from a bag or a box using the laminated material according to the present invention.

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

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

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

FIG. 7 is a schematic configuration diagram illustrating an example of a take-up type vacuum evaporation machine.

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

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Flexible plastic base material 2 Inorganic oxide thin film 3 Coating thin film 4 Printing pattern layer 5 Adhesive layer 6 Heat-sealing resin layer 7 Seal part 8 Adhering part 9 For paper container formation Blank plate 10 Side end portion 11 Side end seal portion 12 Trunk portion 13 Bottom portion 14 Roof type seal portion 8a Sticking portion 9a Blank plate for forming paper container 10a Side end portion 11a Side end seal portion 12a Tube Body 15 Cylindrical bottom plate 15a Bottom 16 Bottom seal 17 Peeling piece 18 Drinking mouth 19 Cylindrical lid plate 19a Lid 20 Upper seal A Laminated material B Three-way seal type soft packaging Container C Roof-type paper packaging container D Cylindrical paper can-like packaging container l Folded crease

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08J 7/04 C23C 14/08 Z 4K030 C23C 14/08 16/40 16/40 B65D 1/00 BF term (Ref.) BA05 CA07 DA01 DA04 4F100 AA17B AA19B AA20B AH03H AH06C AH06H AK01A AK01E AK03E AK06 AK07A AK42A AK48A AK51C AK51D AK51G AL05C AR00D BA05 BA07 BA10A BA10E CA23C CA30C CB02 EH66B EJ38A GB16 GB23 GB66 HB31D JD02 JK10 JK14 JK17A JL01 JL12E JM02B JM02C JN01 4K029 AA11 AA25 BA44 BA46 BC00 BD00 GA03 4K030 BA43 BA44 CA07 CA12 DA08 LA01 LA11

Claims (10)

[Claims] 1. A method according to claim 1, wherein one side of the flexible plastic substrate is
Providing a thin film of an inorganic oxide, further providing a coating thin film of a polyurethane-based resin composition containing a silane coupling agent and a filler on the thin film of the inorganic oxide, further comprising: A laminate having a printed pattern layer provided thereon, and a heat-sealing resin layer provided on the entire surface including the printed pattern layer via an adhesive layer. 2. The method according to claim 1, wherein the flexible plastic substrate comprises a biaxially oriented nylon film, a biaxially oriented polyethylene terephthalate film, or a biaxially oriented polypropylene film. Laminated material. 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 inorganic oxide thin film comprises a deposited film of the inorganic oxide formed by a chemical vapor deposition method. 5. 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. 6. The laminate according to claim 1, wherein the printed pattern layer comprises a printed pattern layer made of an ink composition containing a polyurethane resin as a main component of the vehicle. 7. The laminate according to claim 1, wherein the adhesive layer comprises an adhesive layer for a one-component or two-component curable polyurethane-based laminate. 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 any one of claims 1 to 7, wherein the laminate has a tensile elongation of 50%. 9. The heat sealing resin layer according to claim 1, wherein said heat sealing resin layer comprises a polyolefin resin layer.
8. The laminated material according to 8. 10. A polyurethane resin comprising an inorganic oxide thin film provided on one surface of a flexible plastic substrate, and further comprising a silane coupling agent and a filler on the inorganic oxide thin film. Providing a coating thin film of the composition;
Further, a printing pattern layer is provided on the coating thin film,
Furthermore, on the entire surface including the printed pattern layer, via an adhesive layer,
A packaging container characterized by using a laminated material provided with a heat-sealing resin layer, and forming or laminating the laminated material.