JP2000355068A - Laminate for packaging ham and sausage - Google Patents

Abstract

PROBLEM TO BE SOLVED: To have high barrier properties to oxygen gas, water vapor or the like by a method wherein a base material film and a barrier layer made of a thin inorganic oxide film formed by a plasma chemical vapor-phase growing method are laminated on one side of a sealant base material film in the order named. SOLUTION: On one side of a sealant base material film 2, a barrier layer 4 made of a thin inorganic oxide film 3 formed by a plasma chemical vapor- phase growing method is provided. Further, onto the surface of the barrier layer 4, a base material film 5 is laminated. Or by directing the printed design layer of the base material film 5, on which a desired printed design layer or the like is provided in advance, to the surface of the barrier layer 4, the layer 4 and the film 5 may well be laminated together through a laminating adhesive layer of the like. Accordingly, substances can be seen through and a packaging product of hams, sausages or the like, which can fully satisfy barrier properties to oxygen gas, water vapor or the like can be manufactured.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate for packaging ham and sausage, and more particularly, it has excellent transparency and high barrier properties against oxygen gas or water vapor. The present invention relates to a ham and sausage packaging laminate useful for filling and packaging ham and sausage or processed foods thereof.

[0002]

2. Description of the Related Art Conventionally, packaging materials of various forms having predetermined filling and packaging suitability have been developed and proposed for filling and packaging ham and sausage and further processed foods and the like. ing. Thus, in such packaging materials, particularly, deterioration of the contents, specifically, oxidation, deterioration of components such as proteins and fats and oils contained in the contents is suppressed, and further, taste, In order to maintain good freshness, etc., it is strongly required to have a high gas barrier property (gas barrier property) to prevent the transmission of oxygen gas, water vapor, and other gas that alters the contents such as permeating the packaging material. Is what is being done.
By the way, in recent years, as a barrier material having a high gas barrier property of blocking oxygen gas or water vapor, a physical vapor deposition method such as a vacuum deposition method, a sputtering method, and an ion plating method is applied to the surface of a plastic substrate. (PVD method) or silicon oxide, aluminum oxide, oxide, or the like by utilizing a chemical vapor deposition method (CVD method) such as a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, or a photochemical vapor deposition method. Attention has been paid to a gas barrier film formed by forming a deposited film of an inorganic oxide such as magnesium or the like. In the above-mentioned gas barrier film, usually, as a plastic substrate, for example, a biaxially stretched polyethylene terephthalate film, a nylon film,
Resin films such as an axially stretched polypropylene film and a saponified ethylene-vinyl acetate copolymer film are used. The gas barrier film proposed above is arbitrarily laminated with other plastic films, other substrates and the like to produce laminated materials for packaging in various forms, for example, ham sosage. Further, it is expected to be useful as a packaging material for filling and packaging the processed food and the like.

[0003]

However, in the above gas barrier film, when a biaxially stretched polypropylene film is used as the plastic substrate, for example, the biaxially stretched polypropylene film has, for example, anti-blocking properties. For this reason, since it contains additives, fillers, etc., its surface has a fine uneven shape, and therefore, the surface smoothness is reduced by other base materials (biaxially stretched polyethylene terephthalate). As a result, it is difficult to form a vapor-deposited film of an inorganic oxide on one surface thereof, and it is difficult to form a vapor-deposited film that completely covers the surface in a continuous manner. There is a problem that it is extremely difficult and it is difficult to produce a gas barrier film that is sufficiently satisfactory. Also,
When a biaxially oriented polypropylene film is used as a plastic base material and an inorganic oxide deposited film such as a silicon oxide deposited film is formed on one surface thereof by plasma enhanced chemical vapor deposition, the biaxially oriented polypropylene film is used. There is also a problem that the film is yellowed or browned by the plasma treatment, and furthermore chemically degraded, and it is extremely difficult to produce a colorless and transparent barrier film. Further, when a biaxially stretched polypropylene film is used and a vapor-deposited film of an inorganic oxide such as a silicon oxide vapor-deposited film is formed on one surface thereof by plasma enhanced chemical vapor deposition, the surface of the biaxially-stretched polypropylene film is In addition, a layer (weak boundary) in which a so-called adhesive property is weakened by plasma treatment
(Layer WBL) is generated, which causes a problem that the adhesion strength between the biaxially stretched polypropylene film and the deposited film of the inorganic oxide is insufficient, and the barrier property is not improved. Further, biaxially stretched polypropylene film is inferior in heat resistance, for example, by physical vapor deposition,
When forming a vapor-deposited film of an inorganic oxide, a phenomenon often occurs that the film itself is deteriorated by heating or the like at the time of vapor deposition and a gas barrier film can no longer be manufactured. Further, in the above gas barrier film, generally, on one surface of the plastic substrate, an inorganic oxide deposited film is formed, and then, on the inorganic oxide deposited film surface, gravure printing or the like is performed. In this case, a desired printing pattern layer is provided. At this time, since the gas barrier film passes from the paper supply to the winding side of the printing press, the gas barrier film is provided between various rolls constituting the printing press. There is a problem that pressure or the like is applied to the conductive film, cracks or the like are generated in the vapor deposited film of the inorganic oxide constituting the gas barrier film, and the barrier properties are thereby deteriorated. Further, the deterioration of the gas barrier properties as described above is caused by providing a desired print pattern layer on the gas barrier film and then laminating another petit sticky film or the like, in the laminating step, in the laminating step. In order to pass from the paper feeding to the take-up side, pressurizing roller
There is also a problem that pressure or the like is applied to the gas barrier film between the spaces, and cracks or the like are generated in the vapor deposited film of the inorganic oxide constituting the gas barrier film, thereby deteriorating the barrier properties. Accordingly, the present invention provides a ham and sausage packaging laminate having excellent transparency, and also having a high barrier property against oxygen gas or water vapor and useful for filling and packaging of ham and sausage. Is to provide the body.

[0004]

As a result of various studies to solve the above problems, the present inventor has found that when forming an inorganic oxide vapor-deposited film, a plastic substrate such as a biaxially stretched polypropylene film is used. Focusing on using a sealant base film with excellent surface smoothness instead of using, first, plasma chemical vapor deposition method etc. is used on one side of the sealant base film Then, a vapor-deposited film of the inorganic oxide is formed into a film, and further, on the surface of the vapor-deposited film of the inorganic oxide having the vapor-deposited film of the inorganic oxide formed as described above, A laminate is manufactured by laminating a base film such as a biaxially stretched polypropylene film via an adhesive or the like.
When the sausage or the processed food or the like is filled and packaged, first, at the time of forming a deposited film of an inorganic oxide by plasma enhanced chemical vapor deposition, the deposited film of the inorganic oxide is
On the surface of the sealant base film, continuously, uniformly,
In addition, it can be formed in a state that completely covers the surface, and further, since a base film such as a biaxially stretched polypropylene film is not used as a plastic base material to be formed into a film, the surface is yellowed, or , Browning, and furthermore, prevent chemical or thermal deterioration, etc., and indirectly form a deposited film of inorganic oxide that completely covers the surface of the base film such as the biaxially stretched polypropylene film. It is possible to manufacture a laminate having improved adhesion strength between a base film such as a biaxially stretched polypropylene film and an inorganic oxide vapor-deposited film, and ultimately to see through the contents. The present invention has been completed by finding that a packaged product such as ham and sausage can be manufactured which can be produced and which is sufficiently satisfactory in gas barrier properties against oxygen gas or water vapor.

That is, according to the present invention, a barrier layer composed of a thin film of an inorganic oxide formed by a plasma enhanced chemical vapor deposition method is provided on one surface of a sealant base film, and the surface of the barrier layer is The present invention relates to a laminate for ham and sausage packaging, characterized by having a configuration in which material films are laminated.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. First, the ham sauce according to the present invention is used.
The layer structure of the laminated body for packaging will be described with reference to the drawings by way of specific examples. FIGS. 1, 2 and 3 show the laminated body for ham and sausage packaging according to the present invention. FIG. 4 and FIG. 5 are schematic cross-sectional views showing a layer structure of a ham sausage package using the ham sausage packaging laminate according to the present invention. FIG. 3 is a schematic perspective view showing an example of a packaged product in which is packed and packed.

As shown in FIG. 1, a laminate 1 for packaging ham and sausage according to the present invention has an inorganic oxide film formed on one surface of a sealant base film 2 by a plasma enhanced chemical vapor deposition method. The basic structure is such that a barrier layer 4 made of a thin film 3 is provided, and a base film 5 is further laminated on the surface of the barrier layer 4. A specific example of the laminated body for packaging ham and sausage according to the present invention is as follows. The laminated body 1a for packaging ham and sausage according to the present invention.
As shown in FIG. 2, a barrier layer 4 composed of an inorganic oxide thin film 3 is formed on one surface of a sealant base film 2 by a plasma enhanced chemical vapor deposition method.
The substrate film 5 on which a desired print pattern layer 6 or the like is provided in advance, the print pattern layer 6 is opposed to the surface of the barrier layer 4, and the laminating adhesive layer 7 or the like is formed. It has a configuration in which the layers are interposed. Further, as another example of the laminate for packaging ham and sausage according to the present invention, as shown in FIG. 3, as shown in FIG. In the laminate 1a, the sealant substrate film 2 is made of a co-extruded laminate film 2a made of a polyolefin resin having heat-sealing property and made of two or more of the heat-resistant polyolefin resins. A ham and sausage packaging laminate 1b having a configuration in which a barrier layer 4 composed of an inorganic oxide thin film 3 formed by plasma enhanced chemical vapor deposition on one surface of a film 2a may be used. It is. In FIG. 3 described above,
5, 6, 7 and the like have the same meaning as described above.

[0008] In the present invention, the above-mentioned examples illustrate only 12 examples of the ham and sausage packaging laminate according to the present invention, and the present invention is not limited thereto. It goes without saying that there is nothing. For example, although not shown, in laminating a base film provided with a desired print pattern layer or the like in advance on the surface of the barrier layer, instead of laminating the print pattern layer facing the surface of the barrier layer, a print pattern The layer may not be opposed to the surface of the barrier layer, but may be configured to be laminated via a laminating adhesive layer or the like. In the present invention, although not shown, in addition to the sealant base film, the base film, and the like, further, depending on the purpose of use, the contents to be filled and packaged, the distribution channel, the sales form, the application, and the like, It is possible to design and manufacture various forms of laminates by arbitrarily laminating plastic films and the like.

Next, in the present invention, the ham sausage packaging laminate as described above is used.
An example of a packaged product obtained by filling and packaging a processed food or the like will be described. For example, a packaged product using the ham and sausage packaging laminate 1 shown in FIG. Explaining in an example of packaging, as shown in the perspective view of FIG.
Two laminates 1 and 1 for a package for preparing a sausage are prepared, the surfaces of the sealant base films 2 and 2 located at the innermost layers thereof are superposed on each other, and thereafter, the ham sauce is prepared. -Three-sided seal type soft packaging by heat-sealing the peripheral edges of the three outer peripheries facing the two-layered laminates 1, 1 to form three-sided seal portions 11, 11, 11; The container 12 is manufactured, and then, as shown in the perspective view of FIG. 5, the contents 13 such as ham and sausage are filled through the upper end opening of the container 12 for soft packaging. Heat seal the upper opening to seal.
The container 12 for soft packaging is hermetically sealed by forming a sealing portion 11 ', and the ham sausage is laminated using the ham sausage packaging laminate 1 according to the present invention. A packaged product A in which contents 13 such as are packed and packed can be manufactured. In the present invention, when the contents such as ham and sausage are filled and packaged as described above, for example, gas replacement packaging such as nitrogen gas, or aseptic packaging such as retort treatment and boiling treatment is performed. It goes without saying that it is possible to fill and package using known packaging techniques such as, for example. Further, in the present invention, it is needless to say that the present invention is not limited to the above-illustrated packaged products, and it is needless to say that various forms of packaged products can be manufactured depending on the purpose, use, and the like. That is.

[0010] Next, in the present invention, the material constituting the ham / sausage packaging laminate and the like according to the present invention as described above and the method of producing the same will be described.
Various manufacturing methods and the like can be adopted. First, in the present invention, the ham sauce according to the present invention is used.
First, as a sealant base film, a barrier layer composed of a thin film of an inorganic oxide can be formed by a plasma enhanced chemical vapor deposition method. Resin films or sheets that can be melted by heat and fused to each other can be used. Specifically, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, ethylene / α-olefin copolymer polymerized using a metallocene catalyst, 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 An acid obtained by modifying a polyolefin resin such as coalesced, methylpentene polymer, polybutene polymer, polyethylene or polypropylene with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and itaconic acid. Modified polyolefin resin, polyvinyl acetate resin Poly (meth) acrylic resin, polyvinyl chloride resin, various resins other such film or sheet - may be used and.

In the present invention, the thickness of the resin film or sheet as the above-mentioned sealant base film is appropriately set in view of the stability at the time of production and the like. Is possible, but about 10 μm to 10 μm
0 μm is preferable, and more preferably 20 μm to 50 μm.
The m-th position is desirable. Further, in the present invention, since the above-mentioned sealant substrate film is formed by depositing an inorganic oxide vapor-deposited film on the surface by plasma enhanced chemical vapor deposition, the surface roughness of the film is 10%. 1. Point average roughness
It is preferable to have a surface smoothness within the range of 4 μm or less. Thus, in the present invention, since the sealant base film has the above-mentioned surface smoothness, the deposited film of the inorganic oxide completely covers the surface of the sealant base film. In addition, it has the advantage that the close adhesion is enhanced and the required barrier properties can be sufficiently obtained. In the present invention, the above-mentioned sealant base film preferably has transparency from the viewpoint that contents can be seen through from the outside. Furthermore, in the present invention, among the above-described sealant base films, it is particularly preferable to use a low-density polyethylene, an unstretched polypropylene film, or the like, which has heat resistance among the sealant base films. This is because they are also excellent in sealability, oil resistance, transparency and the like. Further, in the present invention, as the above-mentioned sealant base film, the above-mentioned polyolefin resin having heat sealability is used, and a resin composed of two or more thereof is used in combination. For example, a co-extruded laminated film obtained by co-extrusion using a T-die co-extrusion molding method or a co-extrusion inflation molding method can be used. In this case,
It is preferable because it has a sufficient heat seal property.

Next, in the present invention, a thin film of an inorganic oxide formed by a plasma enhanced chemical vapor deposition method as a barrier layer will be described. It is also possible to use a multilayer film composed of one or more layers of a deposited silicon oxide film (thin film) by plasma enhanced chemical vapor deposition. The silicon oxide deposited film formed by the plasma enhanced chemical vapor deposition method has the formula SiO _x (X represents a number of 0 to 2).
Is a continuous vapor-deposited film mainly composed of silicon oxide represented by the formula:
_X (X represents a number from 1.7 to 2.0) is preferably a thin film mainly composed of a deposited silicon oxide film. The silicon oxide deposited film is at least
It is made of a deposited silicon oxide film containing silicon and oxygen as constituent elements and further containing a trace constituent element of at least one of carbon, hydrogen and oxygen. Further, it is desirable that the above-mentioned silicon oxide vapor-deposited film is a silicon oxide vapor-deposited film containing carbon and having a reduced carbon amount in the depth direction of the vapor-deposited film. Further, in the present invention, the thickness of the deposited silicon oxide film is desirably 1000 ° or less, and specifically, the thickness is 5 °.
It is more preferably about 0 to 500 °, and further preferably 100 to 3 °.
It is desirable that the thickness is about 00 °.
If the thickness is more than 1000 °, furthermore, 500 °, or more than 300 °, cracks or the like are easily generated in the film, which is not preferable. If the thickness is less than 100 °, furthermore, less than 50 °, a barrier effect can be obtained. This is undesirable because it becomes difficult.

In the present invention, the above-mentioned silicon oxide deposited film is specifically formed by a plasma-enhanced chemical vapor deposition method using a low-temperature plasma generator or the like using an organosilicon compound as a monomer gas source for deposition. Can be used. The above-described plasma chemical vapor deposition method will be described more specifically with reference to an example. FIG. 6 is a schematic configuration illustrating an example of a low-temperature plasma chemical vapor deposition apparatus that specifically performs the plasma chemical vapor deposition method. There is a figure. In the present invention, as shown in FIG. 6, the sealant base film 2 is unwound from an unwinding roll 23 disposed in a vacuum chamber 22 of a low-temperature plasma chemical vapor deposition apparatus 21. Runt base film 2
Is conveyed over the peripheral surface of the cooling / electrode drum 25 at a constant speed via the auxiliary roll 24. Then, as described above, the raw material volatile supply devices 26, 27, 2
A mixed gas for vapor deposition comprising an organic silicon compound, oxygen gas, inert gas and the like supplied from 8 is introduced into a vacuum chamber 22 through a raw material supply nozzle 29, and a glow discharge plasma 30 is used to form a vapor deposited film of silicon oxide. Film forming. A predetermined voltage is applied to the cooling / electrode drum 25 from the power supply 31 disposed outside the chamber 22, and a magnet 32 is disposed near the cooling / electrode drum 25. Then, the generation of plasma is promoted to form a silicon oxide vapor-deposited film satisfactorily, and then the sealant base film 2 obtained by forming the silicon oxide vapor-deposited film is used as an auxiliary roll 24. Through the take-up roll 33,
A vapor-deposited inorganic oxide film can be formed on one surface of the sealant substrate film 2 according to the present invention by plasma enhanced chemical vapor deposition. In the drawing, reference numeral 34 denotes a vacuum pump.

In the above, as the organosilicon compound,
For example, 1.1.3.3-tetramethyldisiloxane,
Hexamethyldisiloxane, vinyltrimethylsilane,
Methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltrimethylsilane Ethoxysilane, octamethylcyclotetrasiloxane, and others can be used. In the present invention, among the above-mentioned organosilicon compounds, the use of 1.1.3.3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material is advantageous in terms of handleability and formed deposited film. It is a particularly preferable raw material in view of its characteristics and the like. In the above description, as the inert gas, for example, argon gas, neon gas, or the like can be used, and oxygen gas or the like can be used to supply oxygen. 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.

[0015] The laminate for packaging ham and sauce according to the present invention comprises, as described above, an inorganic oxide formed by a plasma chemical vapor deposition method as a barrier layer on one surface of a sealant base film. By providing the vapor deposited film, a barrier film having a high barrier property against oxygen gas, water vapor and the like can be manufactured. In the present invention, a sealant base film having excellent smoothness, in particular, a low-density polyethylene film, an unstretched polypropylene film, or the like is used, and on one surface thereof, a plasma enhanced chemical vapor deposition method as a barrier layer is used. By forming a vapor-deposited film of an inorganic oxide according to the present invention, there is an advantage that a vapor-deposited film of an inorganic oxide can be easily formed as compared with a biaxially stretched polypropylene film or the like which is inferior in smoothness. This has the advantage that the surface of the film can be completely covered and the barrier properties are extremely improved. Furthermore, in the present invention, the sealant base film, for example, a low-density polyethylene film, an unstretched polypropylene film, etc. are inferior in heat resistance, like the biaxially stretched polypropylene film,
This is to form a deposited film of an inorganic oxide by a plasma chemical vapor deposition method capable of being deposited at a low temperature, thereby forming, for example, a deposited film of an inorganic oxide using a physical vapor deposition method or the like. Degradation or heat shrinkage of the substrate that occurs when
Further, it is intended to prevent a decrease in barrier property and the like due to this. Also, in the present invention, by forming a vapor-deposited film of an inorganic oxide on a sealant substrate film, a substrate film or the like is laminated on the surface of the vapor-deposited film of the inorganic oxide to form a laminate as a packaging material. Uses a sealant base film on which a vapor-deposited film is applied, unlike a base film that produces a large amount of unusable (yet) film in the printing and laminating processes because it is used to manufacture the body Can be
It is also excellent in cost. Thus, in the present invention, the laminate according to the present invention formed into a film as described above has an oxygen permeability of 20 cc / m ² / day (23).
C./90% RH) or lower.

Next, in the present invention, the base film constituting the laminated body for ham and sausage packaging is, for example, a basic material in the case of constituting a packaging container. It has excellent properties in physical, chemical, etc., and in particular, a resin film or sheet having strength, toughness, and heat resistance can be used. Is, for example, a polyester resin,
Films or sheets of tough resins such as polyamide resins, polyaramid resins, polyolefin resins, polycarbonate resins, polystyrene resins, polyacetal resins, fluorine resins, etc. Can be used. Thus, as the resin film or sheet, any one of an unstretched film and a stretched film stretched in a uniaxial or biaxial direction can be used. The thickness of the film is about 5 μm to 100 μm, preferably 10 μm
About 50 μm 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 base film, for example, various paper bases 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.

In the present invention, among the above-mentioned substrate films, it is particularly preferable to use a biaxially oriented polypropylene film. A polypropylene-based resin film or sheet formed of a copolymer with another monomer or a copolymer with another monomer may be used. The resin film or sheet can be used as a single layer or a film formed by a co-extrusion method of two or more layers. About 10 to 10 due to stability
It is desirably about 0 μm, preferably about 20 to 50 μm.

Next, in the present invention, as a material constituting the laminate for packaging ham and sausage according to the present invention, for example, low-density polyethylene, medium-density polyethylene having a barrier property against water vapor, water, etc. , High density polyethylene, linear low density polyethylene, polypropylene, ethylene-
Film or sheet of a resin such as a propylene copolymer,
Alternatively, a colorant such as a pigment may be added to a film or sheet of a resin such as polyvinyl alcohol or a saponified ethylene-vinyl acetate copolymer having a barrier property against oxygen and water vapor, and a coloring agent such as a pigment to the resin. It is possible to use various colored resin films or sheets having light-shielding properties obtained by adding an agent and kneading to form a film. These materials can be used alone or in combination of two or more. The thickness of the above-mentioned film or sheet is arbitrary, but usually 5 μm to 300 μm.
And more preferably about 10 μm to 100 μm.

In the present invention, since the packaging container is usually subjected to severe physical and chemical conditions, strict packaging suitability is required for the packaging material constituting the packaging container. And various conditions such as deformation prevention strength, drop impact strength, pinhole resistance, heat resistance, sealability, quality maintenance, workability, hygiene, etc. are required. Any material that satisfies the above conditions can be selected and used.Specifically, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, Ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid or methacrylic acid copolymer, Chillpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, poly (meth) acrylic resin, polyacrylonitrile resin, Polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin, polycarbonate resin, polyvinyl alcohol Resin, saponified ethylene-vinyl acetate copolymer, fluororesin,
It can be arbitrarily selected from known resin films or sheets such as diene resins, polyacetal resins, polyurethane resins, nitrocellulose and others. In addition, for example, a film such as cellophane, synthetic paper, or the like can be used. In the present invention, the above-mentioned film or sheet 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.

Next, a method of manufacturing a ham / sausage packaging laminate using the above-described materials in the present invention will be described. Laminating methods such as wet lamination, dry lamination, solventless dry lamination, extrusion lamination,
T-die extrusion molding method, co-extrusion lamination method,
Inflation method, co-extrusion inflation method,
It can be performed by others. In the present invention, when performing the above-mentioned lamination, if necessary, for example, a corona treatment, an ozone treatment, a framing treatment, and other pre-treatments can be performed on the film. , An isocyanate-based (urethane-based), polyethyleneimine-based, polybutadiene-based, organic titanium-based anchor coating agent and the like can be used arbitrarily. Thus, in the present invention, in order to produce the ham and sausage packaging laminate according to the present invention, for example, polyurethane-based, polyacryl-based, polyester-based, epoxy-based, polyvinyl acetate-based, A lamination method by dry lamination using a cellulose-based or other laminating adhesive or the like, and dry laminating through the laminating adhesive layer, comprises a base film and an inorganic oxide. Is most preferable because it has a good adhesion to a deposited film of the above.

Next, in the present invention, a method of making a bag or a box using the above-described ham and sausage packaging laminate according to the present invention will be described. In the case of a soft packaging bag made of a plastic film or the like, a laminate for ham and sausage packaging produced by the above method is used, and the surface of the sealant base film of the inner layer is opposed to the laminate. The bag can be formed by folding the sheet or stacking the two sheets, and further heat sealing the peripheral end to provide a seal portion. Thus, as a bag making method, the above-mentioned ham and sausage packaging laminate is folded with its inner layer facing the surface, or two of them are overlapped, and further, the periphery of the outer periphery is The end portions are formed, for example, as side seal type, two-way seal type, three-way seal type, four-way seal type, envelope-attached seal type, and gasket-attached seal type (pyro-seale). ), Heat seals such as pleated seal type, flat bottom seal type, square bottom seal type, etc., and various forms of packaging according to the present invention. Container can be manufactured. In addition, for example, a self-standing packaging bag (standing pouch) or the like can be manufactured. In the present invention, a tube container or the like can also be manufactured using the above-described laminated material. In the above, as a method of the heat seal, for example, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, an ultrasonic seal, or the like is used. Can be performed in the following manner. 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.

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

In the present invention, the packaging container produced as described above is excellent in transparency, barrier properties against oxygen, water vapor, etc., impact resistance, and the like. It has the suitability for post-processing such as box making, and also prevents peeling of the deposited thin film as a barrier film, and also prevents the occurrence of thermal cracks, and prevents its deterioration, and Demonstrate excellent resistance as a ham
It is excellent in filling and packaging suitability, preservation suitability and the like of various articles such as sausage or processed food and others.

[0025]

Now, the present invention will be described in further detail with reference to specific examples. Example 1 (1). A linear low-density polyethylene film having a thickness of 30 μm was used, and was mounted on a delivery roll of a plasma-enhanced chemical vapor deposition apparatus, and a silicon oxide vapor-deposited film having a thickness of 120 ° was formed under the following conditions. A conductive film was produced. Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 10: 2 (unit: slm, standard driitter minit, standardlitt)
er minute) Degree of vacuum in vacuum chamber: 5.0 × 10 ⁻⁶ mbar Degree of vacuum in evaporation chamber: 6.0 × 10 ⁻² mbar Cooling / electrode drum supply power: 30 kW Film transport speed: 150 m / Evaporation surface: Corona treated surface Thickness of vapor deposition film: 120Å (X-ray fluorescence analysis) (2). A plasma treatment was performed on the surface of the silicon oxide deposited film of the barrier film produced above under the following conditions. As a result, the surface tension of the surface of the deposited silicon oxide film was 41 dyn.
To 62 dyn. Output: 9 Kw Processing speed: 300 m / min (3). Next, a biaxially-stretched polypropylene film having a thickness of 20 μm was used and attached to one of the delivery rolls of a dry laminator coater. -Attach it to the other delivery roll of the toe coater, then
The biaxially oriented polypropylene film was opposed to the plasma-treated surface of the plasma-treated barrier film, and both were dry-laminated under the following conditions to produce a laminate according to the present invention. Adhesive: Use urethane-based adhesive (Main agent) Takenet A-515 (manufactured by Takeda Pharmaceutical Co., Ltd., trade name) (Curing agent) Takenet A-50 (manufactured by Takeda Pharmaceutical Co., Ltd., trade name) (Solvent) Ethyl acetate (Mixing ratio) Main agent: Curing agent: Solvent = 10: 1: 100 (% by weight) (Coat amount) 4.0 g / m ² (Dry) (4). Next, using the laminate produced above, the low-density polyethylene film surface is superposed facing each other,
The three sides are heat-sealed to produce a three-sided seal-type soft packaging bag. Thereafter, the bag is filled with a sausage, and then subjected to boiling treatment. And produced packaging products. The packaged product produced above was excellent in gas barrier properties against oxygen gas, water vapor, etc., was not deteriorated in the contents, had long-term storage suitability, and was able to see through the contents. .

Embodiment 2 (1). A linear low-density polyethylene film having a thickness of 30 μm was used, and was mounted on a delivery roll of a plasma-enhanced chemical vapor deposition apparatus, and a silicon oxide vapor-deposited film having a thickness of 120 ° was formed under the following conditions. A conductive film was produced. Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 10: 2 (unit: slm, standard driitter minit, standardlitt)
er minute) Degree of vacuum in vacuum chamber: 5.0 × 10 ⁻⁶ mbar Degree of vacuum in evaporation chamber: 6.0 × 10 ⁻² mbar Cooling / electrode drum supply power: 30 kW Film transport speed: 150 m / Evaporation surface: Corona treated surface Thickness of vapor deposition film: 120Å (X-ray fluorescence analysis) (2). A plasma treatment was performed on the surface of the silicon oxide deposited film of the barrier film produced above under the following conditions. As a result, the surface tension of the surface of the deposited silicon oxide film was 41 dyn.
To 62 dyn. Output: 9 Kw Processing speed: 300 m / min (3). Next, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used,
Attach it to one of the rolls of the toe coater machine,
The plasma-treated barrier film is mounted on the other delivery roll of the dry laminator coater, and then the above-mentioned biaxial stretching is performed on the plasma-treated surface of the plasma-treated barrier film. The polyethylene terephthalate film was opposed to each other, and both were dry-laminated under the following conditions to produce a laminate according to the present invention. Adhesive: Use urethane-based adhesive (Main agent) Takenet A-515 (manufactured by Takeda Pharmaceutical Co., Ltd., trade name) (Curing agent) Takenet A-50 (manufactured by Takeda Pharmaceutical Co., Ltd., trade name) (Solvent) Ethyl acetate (Mixing ratio) Main agent: Curing agent: Solvent = 10: 1: 100 (% by weight) (Coat amount) 4.0 g / m ² (Dry) (4). Next, using the laminate produced above, the low-density polyethylene film surface is superposed facing each other,
The three sides are heat-sealed to produce a three-sided seal-type soft packaging bag. Thereafter, the bag is filled with a sausage, and then subjected to boiling treatment. And produced packaging products. The packaged product produced above was excellent in gas barrier properties against oxygen gas, water vapor, and the like, did not show any alteration of the contents, had long-term storage suitability, and was able to see through the contents.

Embodiment 3 (1). An unstretched polypropylene film having a thickness of 30 μm is used, and is mounted on a delivery roll of a plasma enhanced chemical vapor deposition apparatus, and a silicon oxide deposited film having a thickness of 120 ° is formed under the following conditions to form a barrier film. Was manufactured. Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 10: 2 (unit: slm, standard driitter minit, standardlitt)
er minute) Degree of vacuum in vacuum chamber: 5.0 × 10 ⁻⁶ mbar Degree of vacuum in evaporation chamber: 6.0 × 10 ⁻² mbar Cooling / electrode drum supply power: 30 kW Film transport speed: 150 m / Evaporation surface: Corona treated surface Thickness of vapor deposition film: 120Å (X-ray fluorescence analysis) (2). A plasma treatment was performed on the surface of the silicon oxide deposited film of the barrier film produced above under the following conditions. As a result, the surface tension of the surface of the deposited silicon oxide film was 41 dyn.
To 62 dyn. Output: 9 Kw Processing speed: 300 m / min (3). Next, a biaxially-stretched polypropylene film having a thickness of 20 μm was used and attached to one of the delivery rolls of a dry laminator coater. -Attach it to the other delivery roll of the toe coater, then
The biaxially oriented polypropylene film was opposed to the plasma-treated surface of the plasma-treated barrier film, and both were dry-laminated under the following conditions to produce a laminate according to the present invention. Adhesive: Use urethane-based adhesive (Main agent) Takenet A-515 (manufactured by Takeda Pharmaceutical Co., Ltd., trade name) (Curing agent) Takenet A-50 (manufactured by Takeda Pharmaceutical Co., Ltd., trade name) (Solvent) Ethyl acetate (Mixing ratio) Main agent: Curing agent: Solvent = 10: 1: 100 (% by weight) (Coat amount) 4.0 g / m ² (Dry) (4). Next, using the laminate produced above, the unstretched polypropylene film faces are superimposed on each other, and the three sides are heat-sealed to produce a three-sided seal-type soft packaging bag. Thereafter, the bag was filled with a sausage and packaged, followed by boiling treatment to produce a packaged product. The packaging products produced above are oxygen gas,
It was excellent in gas barrier properties against water vapor and the like, did not show any alteration of the contents, had long-term storage suitability, and was able to see through the contents.

Comparative Example 1 (1). A biaxially stretched polypropylene film having a thickness of 20 μm was used, which was mounted on a delivery roll of a plasma enhanced chemical vapor deposition apparatus, and a 140 ° -thick silicon oxide vapor-deposited film was formed under the following conditions. A film was produced. Reaction gas mixing ratio: hexamethyldisiloxane: oxygen gas: helium = 1.5: 20: 2 (unit: slm, standard dritting unit, standard l)
itter minute) The degree of vacuum in the vacuum chamber: 1.0 × 10 ⁻⁶ mbar The degree of vacuum in the evaporation chamber: 9.0 × 10 ⁻² mbar Cooling / electrode drum supply power: 30 kW Film transport speed: 100 m / Evaporation surface: Corona treated surface Thickness of evaporation film: 130Å (X-ray fluorescence analysis) (2). A plasma treatment was performed on the surface of the silicon oxide deposited film of the barrier film produced above under the following conditions. As a result, the surface tension of the surface of the deposited silicon oxide film was 39 dyn.
To 60 dyn. Output: 9 Kw Processing speed: 300 m / min (3). Next, a low-density polyethylene film having a thickness of 30 μm was used and mounted on one of the delivery rolls of a dry laminator coater. Toco
The other low-density polyethylene film was attached to the other delivery roll of the turbomachine, and then the low-density polyethylene film was opposed to the plasma-treated surface of the plasma-treated barrier film.
Both were dry-laminated under the following conditions to produce a laminate. Adhesive: Use urethane-based adhesive (Main agent) Takenet A-515 (manufactured by Takeda Pharmaceutical Co., Ltd., trade name) (Curing agent) Takenet A-50 (manufactured by Takeda Pharmaceutical Co., Ltd., trade name) (Solvent) Ethyl acetate (Mixing ratio) Main agent: Curing agent: Solvent = 10: 1: 100 (% by weight) (Coat amount) 4.0 g / m ² (Dry) (4). Next, using the laminate produced above, the low-density polyethylene film surface is superposed facing each other,
The three sides are heat-sealed to produce a three-sided seal-type soft packaging bag. Thereafter, the bag is filled with a sausage, and then subjected to boiling treatment. And produced packaging products. The packaged product produced above lacked gas barrier properties against oxygen gas, water vapor and the like, was slightly sticky to the contents, and lacked long-term storage suitability.

Experimental Example The following data was measured for each of the laminates manufactured in Examples 1 to 3 and Comparative Example 1. (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)]. (3). Measurement of Laminate Strength This was measured for the laminate with a width of 15 mm using Tensilon (tensile speed: 50 mm / min). (4). Measurement of surface smoothness This is 30 μm thick as a sealant base film.
Of a low-density polyethylene film and a biaxially stretched polypropylene film having a thickness of 20 μm. The measuring method is a three-dimensional surface roughness measuring device (manufactured by Tokyo Seimitsu Co., Ltd.
The measurement was performed using a model name (Surfcom 590A-3DF). The surface roughness was evaluated by a 10-point average value (Rs). The measurement results of the above (1), (2), and (3) are shown in Table 1 below, and the measurement results of the above (4) are shown in Table 2 below.

[0030] In Table 1 above, the oxygen permeability is [cc / m ² / d
ay · 23 ° C. · 90% RH], the water vapor permeability is a unit of [g / m ² / day · 40 ° C. · 100% RH], and the laminating strength is measured in Example 1. 3 are the laminate strengths between the adhesive layer and the vapor-deposited film, and those of Comparative Example 1 are the laminate strengths of the biaxially stretched polypropylene film itself. It is a unit of [gf / 15 mm width].

[0031]

As is evident from the results shown in Tables 1 and 2 above, those of Examples 1 to 3 were excellent in oxygen permeability, water vapor permeability, laminate strength and the like. Comparative Example 1 was inferior. In particular, in oxygen permeability, a significant difference was observed between Examples 1 to 3 and Comparative Example 1. In the laminate strength, the laminate of Comparative Example 1 showed a phenomenon of delamination in the biaxially stretched polypropylene film itself as the base film. From the above, it was found that forming an inorganic oxide vapor-deposited film on the sealant base film was superior in oxygen permeability and water vapor permeability. Next, as is clear from the results shown in Table 2 above, it was confirmed that the smoothness of the low-density polyethylene fill was higher than that of the biaxially stretched polypropylene film.

[0033]

As is apparent from the above description, the present invention has an excellent surface smoothness in forming an inorganic oxide deposited film, instead of using a plastic substrate such as a biaxially stretched polypropylene film. First, a vapor-deposited inorganic oxide film was formed on one surface of the sealant substrate film using plasma-enhanced chemical vapor deposition or the like. A biaxially oriented polypropylene is formed on the surface of the inorganic oxide vapor-deposited film of the sealant base film having the inorganic oxide vapor-deposited film formed above by laminating adhesive or the like. When a laminate is manufactured by laminating a base film such as a film, and then using the laminate, ham and sausage or a processed food and the like are filled and packaged. Inorganic oxide by chemical vapor deposition Upon formation of a vapor-deposited film, the vapor-deposited film of the inorganic oxide can be formed on the surface of the sealant substrate film continuously, uniformly, and in a state of completely covering the surface, Furthermore, since a base film such as a biaxially oriented polypropylene film is not used as a plastic base material to be formed into a film, yellowing or browning of the surface, and furthermore, prevention of chemical or thermal deterioration, etc. And, indirectly, can form a vapor-deposited film of inorganic oxide that completely covers the surface of the base film such as the biaxially oriented polypropylene film, and the base film such as the biaxially oriented polypropylene film It is possible to manufacture a laminated body with an improved adhesion strength with a deposited film of inorganic oxide and inorganic oxide, and in the end, can see through the contents and has a sufficient gas barrier property against oxygen gas or water vapor. Satisfactory Ham source - Se - is that it can be produced packaging products di like. In the present invention, in particular, even if an inorganic oxide vapor-deposited film is formed on the surface of a base film such as a biaxially stretched polypropylene film having a poor surface smoothness by a plasma enhanced chemical vapor deposition method, it does not react with oxygen gas or water vapor. Oxygen gas or water vapor can be obtained by forming an inorganic oxide vapor-deposited film by plasma enhanced chemical vapor deposition on the surface of a sealant base film that does not provide sufficient barrier properties but has excellent surface smoothness. This has the advantage that a barrier film having excellent barrier properties against water, particularly excellent in barrier properties against oxygen gas, can be produced. Further, in the present invention, an inexpensive vapor deposition material such as an organic silicon compound is used, and further, at a low vacuum, a plasma-enhanced chemical vapor deposition method can form an inorganic oxide vapor deposition film. This reduces the manufacturing cost. Furthermore, in the present invention, since a vapor-deposited film of an inorganic oxide is formed on the surface of a sealant base film such as a low-density polyethylene film or an unstretched polypropylene film, Compared to forming a vapor-deposited film of an inorganic oxide, it is excellent in barrier properties or cost.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing a layer configuration of an example of a ham / sausage packaging laminate according to the present invention.

FIG. 2 is a cross-sectional view showing a layer configuration of an example of the laminate for packaging ham and sausage according to the present invention.

FIG. 3 is a cross-sectional view showing a layer configuration of an example of the ham / sausage packaging laminate according to the present invention.

FIG. 4 is a perspective view showing an example of a packaged product in which contents such as ham and sausage are filled and packaged using the laminate for ham and sausage packaging according to the present invention.

FIG. 5 is a perspective view showing an example of a packaged product in which contents such as ham and sausage are filled and packaged using the laminate for packaging ham and sausage according to the present invention.

FIG. 6 is a configuration diagram showing a schematic configuration of a plasma chemical vapor deposition apparatus.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Laminated body for ham and sausage packaging 1a Laminated body for ham and sausage packaging 1b Laminated body for ham and sausage packaging 2 Sealant base film 3 Thin film of inorganic oxide 4 Barrier layer 5 Base film 6 Printed picture layer 7 Seal portion 11 Seal portion 11 'Upper end seal portion 12 Three-way seal type flexible packaging container 13 Contents A Packaging product

 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 3E086 AD01 BA04 BA15 BA33 BA40 BB01 BB22 BB62 CA04 4F006 AA02 AA04 AA12 AA13 AA14 AA15 AA16 AA17 AA18 AA19 AA20 AA22 AA32 AA35 AA36 AA37 AA01 AB ABA ABA ABA ABA AA ABA AA ABA AA A A A B A A A A A A B A A A A A A A B A A A B A A AK01C AK03A AK03D AK06A AK07A AK07C AK42C AK51G AK63 AR00E BA03 BA04 BA05 BA07 BA10A BA10C BA10E BA44 CB02 DD07A EH20A EH20D EH66B EJ38C EJ61B GB17 GB23 HB31E JD02B JD03 JD04 JK06 JK15A JL12A JL12D JM02B JN01 JN28 YY00 YY00A YY00B 4K030 AA06 AA09 AA14 AA16 BA24 BA27 BA29 BA44 CA07 CA11 CA12 DA08 FA01 JA01 LA01 LA24

Claims (13)

[Claims] Claims (1)
A ham sausage package comprising a barrier layer made of a thin film of an inorganic oxide formed by plasma enhanced chemical vapor deposition, and a base film laminated on the surface of the barrier layer. For laminate. 2. The surface roughness of the sealant substrate film is as follows:
The ham and sausage packaging laminate according to claim 1, wherein the laminate has a surface smoothness in a range of 1.4 µm or less in 10-point average roughness Rs. 3. The laminate for packaging ham and sausage according to claim 1, wherein the sealant base film comprises a low-density polyethylene film or an unstretched polypropylene film. . 4. The method according to claim 1, wherein the sealant base film is a heat-sealing material.
The laminate for ham and sausage packaging according to any one of claims 1 to 3, wherein the laminate is formed from a co-extruded laminate film composed of two or more polyolefin-based resins having heat resistance. 5. A barrier layer comprising a thin film of an inorganic oxide,
A barrier layer made of a thin film of silicon oxide, and the thin film of silicon oxide further contains at least one compound of one or more of elements consisting of carbon, hydrogen, silicon, and oxygen. Claims 1 to 3 characterized by the above-mentioned.
4. The laminate for packaging ham and sausage according to 4. 6. The ham barrier layer according to claim 1, wherein the barrier layer made of a thin film of silicon oxide is a barrier layer made of a deposited film of silicon oxide formed by plasma enhanced chemical vapor deposition. A laminate for sausage packaging. 7. A barrier layer comprising a deposited silicon oxide film,
The ham soot according to any one of claims 1 to 6, wherein silicon and oxygen are contained as constituent elements, and one or more elements of carbon, hydrogen or oxygen are contained as trace constituent elements. A laminate for sage packaging; 8. A barrier layer comprising a thin film of an inorganic oxide,
The ham sausage packaging laminate according to any one of claims 1 to 7, wherein the laminate contains carbon and the amount of carbon decreases in the depth direction of the barrier layer. 9. A barrier layer comprising a thin film of an inorganic oxide,
The ham / sausage packaging laminate according to any one of claims 1 to 8, wherein the film thickness is 500 ° or less. 10. An oxygen permeability of 20 cc / m ² / da
The laminate for ham and sausage packaging according to any one of claims 1 to 9, wherein the temperature is not more than y (23 ° C / 90% RH). 11. The base film is a biaxially oriented polypropylene film or a biaxially oriented polyethylene terephthalate.
2. The film according to claim 1, which is a film.
0. The laminate for packaging ham and sausage described in 0. 12. The method according to claim 1, wherein the base film has a structure in which a printed pattern layer is provided in advance.
12. The laminate for packaging ham and sausage described in 11 above. 13. The laminate for packaging ham and sausage according to claim 1, wherein the base film is formed by laminating by a dry laminating method.