JP2002019005A - Packaging material for tube container and tube container with use of it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a packaging material for a tube container which has strength, etc., is excellent in heat resistance, moisture-proofing properties, heat- sealing properties, pinhole resistance, stab resistance, transparency, etc., excellent in gas-barrier properties for preventing the permeation of oxygen gas, water vapor, etc., has an aptitude for packing/packaging/preserving contents, does not generate harmful substances, etc., when subjected to incineration disposal treatment after being used, and is excellent in disposal treatment aptitude, environmental aptitude, etc., and the tube container with the use of it. SOLUTION: The packaging material in which a polyolefin resin surface layer, a resin film having a vapor-deposition film of an inorganic oxide, and a polyolefin resin back layer are laminated in turn and the tube container with the use of it are disclosed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wrapping material for a tube container and a tube container using the same, and more particularly, to a heat-resistant, moisture-proof, heat-resistant material having strength and the like. -Excellent rollability, pinhole resistance, puncture resistance, transparency, etc., and excellent barrier properties to prevent the transmission of oxygen gas, water vapor, etc. Further, the present invention relates to a tube container packaging material which is extremely excellent in disposal suitability and environmental suitability without generating harmful substances when incinerated and disposed of after use, and a tube container using the same. Things.

[0002]

2. Description of the Related Art Conventionally, tube containers have been manufactured by various methods. One of them is to laminate at least a surface resin layer, an intermediate layer, and an inner resin layer sequentially. Then, using the laminated material, the surface of the surface resin layer at both ends and the surface of the inner resin layer are overlapped, and the opposite surface is heat-sealed to form a cylindrical body. A method of manufacturing a tube container by forming a head having a mouth, a shoulder, and the like at one opening of the cylindrical body, and then screwing a cap onto the head. is there. Thus, the tube container manufactured as described above is supplied with, for example, toothpaste, mayonnaise, wasabi, and the like from the other opening of the cylindrical body.
Fill with knead, ketchup and other seasonings, or whipped cream and other creams and other foods and beverages, cosmetics, pharmaceuticals, and other contents and then open the contents. Parts are hermetically sealed to form a bottom seal part, and various forms of packaged products comprising tube containers are manufactured. By the way, in the laminated material for producing the above-mentioned tube container, various plastic films and the like are laminated from the viewpoint of protecting the contents filled and packed in the tube container to constitute the laminated material. However, among them, particularly, a barrier material having an excellent gas barrier property for preventing permeation of oxygen gas, water vapor and the like, and an excellent moisture-proof property and the like are laminated. The barrier material is usually a polyvinylidene chloride-based resin monolayer film, a co-extruded film using a polyvinylidene chloride-based resin, or a coated film made of a polyvinylidene chloride-based resin composition. Is used. In addition, an ethylene-vinyl alcohol copolymer film or the like is also used as a barrier material.

[0003]

However, as described above, in a tube container using a polyvinylidene chloride resin as a barrier material, a gas barrier property for preventing permeation of oxygen gas, water vapor and the like is required. Although it has the expected effect, if the tube container is used as a packaging container and then disposed of as garbage, for example, if it is disposed of by incineration, etc., it must contain chlorine atoms. Therefore, during incineration and disposal, for example, it causes toxic gas such as dioxin, etc., and is likely to affect the human body. Etc. also has a problem that it lacks. Further, in a tube container using the above-mentioned ethylene-vinyl alcohol copolymer film as a barrier material, in a completely dry state, a gas barrier property for preventing permeation of oxygen gas, water vapor and the like is required. Although it has a period effect, in the wet state,
The gas barrier property that prevents the transmission of oxygen gas, water vapor, etc.
There is a problem in that the temperature is remarkably reduced and can no longer be used. Therefore, the present invention has strength and the like, and is excellent in heat resistance, moisture resistance, heat sealability, pinhole resistance, piercing resistance, transparency and the like. Excellent barrier properties to prevent permeation, suitability for packing and preserving the contents, and suitability for disposal and environmental protection Chu with excellent
An object of the present invention is to provide a packaging material for a tube container and a tube container using the same.

[0004]

Means for Solving the Problems The present inventor has made various studies to solve the above-mentioned problems, and as a result, provided a deposited film of an inorganic oxide such as silicon oxide and aluminum oxide as a barrier material. Focusing on a barrier film composed of a resin film, and further focusing on the medium use of the barrier film, first, at least, a surface polyolefin-based resin layer, the barrier film described above, and a back polyolefin-based resin layer Are sequentially laminated to produce a tube container wrapping material. The tube container wrapping material is used, and the outermost surface of both ends of the tube container wrapping material is used. The surface of the polyolefin-based resin layer and the surface of the back polyolefin-based resin layer, which is the innermost layer, are overlapped with each other, and the opposing surface is heat-sealed to form a cylindrical body. One opening, shoulder A head portion having a mouth portion is provided, and a cap is screwed onto the head portion to manufacture a tube container. Thus, the content is obtained from the other opening portion of the cylindrical body constituting the tube container. The object is filled and then the opening is sealed.
When a packaged product consisting of a tube container is manufactured by forming a bottom seal portion by heat sealing, it has strength and the like, and is heat-resistant, moisture-proof, heat-sealed, and pin-hole-resistant. It has excellent barrier properties to prevent permeation of oxygen gas, water vapor, etc., and has the suitability for filling and packaging the contents, the suitability for storage, etc., and also after use. A wrapping material for a tube container, which does not generate harmful substances when incinerating a bag-shaped container body or the like made of a bag for flexible packaging and is extremely excellent in disposal suitability and environmental suitability, and using the same. The present invention has been completed by finding that a tube container can be manufactured.

[0005] That is, the present invention provides a tube container package characterized by sequentially laminating a front polyolefin resin layer, a resin film having an inorganic oxide vapor deposited film, and a back polyolefin resin layer. The present invention relates to a material and a tube container using the same.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION A tube container packaging material according to the present invention and a tube container using the same will be described below in more detail with reference to the drawings. First, the layer structure of the tube container packaging material according to the present invention will be described with reference to the drawings. FIG. 1 shows the layer structure of the tube container packaging material forming the tube container according to the present invention. FIG. 2 is a schematic half sectional view showing the structure of a tube container according to the present invention manufactured using the tube container packaging material shown in FIG. .

First, as a packaging material A for a tube container according to the present invention, as shown in FIG. 1, a resin having at least a surface polyolefin resin layer 1 and an inorganic oxide vapor-deposited film 2 from the outside is used. The basic structure is that the film 3 and the back surface polyolefin-based resin layer 1a are sequentially laminated. Thus, the above-described tube container packaging material is merely an example, and the present invention is not limited to the tube container packaging material having the above-described configuration. Instead, various types of tube container packaging materials can be used. For example, although not shown, a layer made of another material can be provided between the respective layers depending on the use, the contents to be filled, and the like, and the layers can be arbitrarily stacked in a laminating order. is there. Further, for example, although not shown, the inorganic oxide of the resin film having the inorganic oxide vapor-deposited film may be laminated by facing in any direction such as the inner surface side or the outer surface side. is there.

Next, in the present invention, an example of manufacturing the tube container according to the present invention by using the above-mentioned tube container packaging material according to the present invention will be described with reference to FIG.
FIG. 2 is a schematic half sectional view showing a configuration of a tube container B according to the present invention manufactured using the tube container packaging material A shown in FIG. 1. In the present invention, as shown in FIG. 2, first, the packaging material A for a tube container according to the present invention produced above is used, for example, using a flexographic ink composition, and by using a flexographic printing method, After forming a print pattern layer (not shown) by flexographic printing of figures, symbols, patterns, etc., the packaging material A for a tube container according to the present invention on which the print pattern layer is formed is rolled up. The surface of the outermost polyolefin-based resin layer 1 as the outermost layer at both ends of the tube container packaging material A and the surface of the rearmost polyolefin-based resin layer 1a as the innermost layer are overlapped, and the polymerized end thereof is welded. A welded portion 11 is formed to produce a tubular body 12, and the tubular body 12 is used as a body constituting a tube container according to the present invention. Next, in the present invention, the shoulder 13 and the mouth 1 constituting the tube container B according to the present invention are provided above one opening of the cylindrical body 12 manufactured as described above.
A head 15 made of 4 or the like is formed according to a conventional method, and thereafter, a cap 16 for sealing is attached to the mouth portion 14 of the head 15 formed as described above.
Is to manufacture. Thus, in the present invention, the tube container R according to the present invention manufactured as described above is filled with the contents such as toothpaste and others through the other opening of the cylindrical body 12 constituting the tube container R. 17 is filled and packaged in an appropriate amount, and then the opening is welded to form a bottom welded portion 18 and the contents 17 are filled and packaged according to the present invention.
The packaging product Ra including the container R can be manufactured. The above-described examples are merely examples of the tube container according to the present invention, and the present invention is not limited thereto.

Next, in the present invention, the material constituting the tube container packaging material, the tube container, and the like according to the present invention, the manufacturing method, and the like will be described. First, in the present invention, as a material constituting the surface polyolefin-based resin layer, as described above, the tube container wrapping material according to the present invention is rolled, and the polymerized end thereof is welded to form a cylindrical body. From manufacturing,
It can be melted and fused to each other by heating.
It is desirable to use a heat-sealing resin capable of forming a print pattern layer by a gravure printing method, a flexographic printing method, or the like. Specifically, the above-mentioned heat
Examples of the resin having a sealing property include low-density polyethylene (LDPE) and medium-density polyethylene (MDP).
E), high density polyethylene (HDPE), linear (linear) low density polyethylene (LLDPE), polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-acrylic acid Ethyl copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, polybutene polymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid Copolymer, an acid-modified polyolefin resin obtained by acid-modifying a polyolefin resin such as polyethylene or polypropylene using an unsaturated carboxylic acid,
Other resins can be used.

Further, in the present invention, as the material constituting the above-mentioned surface polyolefin resin layer, an ethylene-α-olefin copolymer polymerized using a metallocene catalyst (single-site catalyst) is particularly used. Can be. Examples of the ethylene-α-olefin copolymer polymerized using the above metallocene catalyst include, for example, a catalyst obtained by combining a metallocene complex and an alumoxane such as a catalyst obtained by combining zirconocene dichloride and methylalumoxane, that is, a metallocene catalyst. Ethylene-α-olefin copolymers obtained by polymerization can be used. Metallocene catalysts are called multi-site catalysts, whereas current catalysts have heterogeneous active sites.
Since the active sites are uniform, it is also called a single-site catalyst. Specifically, the product name “Kernel” manufactured by Mitsubishi Chemical Corporation, the product name “Evolu” manufactured by Mitsui Petrochemical Industry Co., Ltd., and the product name “Exact” manufactured by Exxon Chemical Co., USA (EXACT) ", Dow Chemical, USA (DO
W CHEMICAL) brand name “Affinity-
(AFFINITY), brand name "ENGAGE (ENGA
GE) "and the like, and an ethylene-α-olefin copolymer polymerized using a metallocene catalyst can be used.

In the present invention, the surface polyolefin-based resin layer contains, for example, one or two or more of the above-mentioned resins having heat sealability as main components. The resin composition is prepared by arbitrarily adding additives and the like, and then the resin composition prepared above is used.
The surface polyolefin-based resin layer can be formed by molding a film or a sheet using other molding methods. Thus, in the present invention, as the surface polyolefin resin layer, for example, an uneven surface called a fish eye is smoothed and flattened, thereby making it possible to perform printing by a gravure printing method or a flexographic printing method. Can greatly improve the quality of the printed picture layer, prevent the occurrence of ink loss, etc., and form a very beautiful printed picture layer, etc., and improve the occurrence of defective products due to print quality. It is desirable to do so. In the present invention, the thickness of the surface polyolefin-based resin layer is desirably about 25 μm to 300 μm, preferably about 30 μm to 200 μm.

Next, in the present invention, the material constituting the back polyolefin resin layer may be any material which can be melted by heat and adhere to each other similarly to the material constituting the above-mentioned front polyolefin resin layer. For example, low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear (linear) low density polyethylene (LLDPE), polypropylene, ethylene-vinyl acetate copolymer, Ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, methyl pentene polymer, polyolefin resin such as polyethylene or polypropylene Acrylic acid, methacrylic acid, maleic acid, maleic anhydride One or more resins such as acid-modified polyolefin resins, polyvinyl acetate resins, polyester resins, polystyrene resins, etc. modified with an unsaturated carboxylic acid such as acid, fumaric acid, itaconic acid, etc. Can be used.

Further, in the present invention, the metallocene catalyst (single-site catalyst) is used as the material constituting the back polyolefin resin layer in the same manner as the material constituting the front polyolefin resin layer. An ethylene-α-olefin copolymer can be used. Ethylene polymerized using the above metallocene catalyst
Examples of the α-olefin copolymer include, for example, a catalyst obtained by using a metallocene complex such as a catalyst obtained by combining zirconocene dichloride and methylalumoxane and an alumoxane, that is, ethylene-α · obtained by polymerization using a metallocene catalyst. Olefin copolymers can be used. The metallocene catalyst has a non-uniform active site and is called a multi-site catalyst, whereas the existing catalyst is called a single-site catalyst because the active site is uniform. Specifically, Mitsubishi Chemical Co., Ltd. product name "Kernel", Mitsui Petrochemical Industry Co., Ltd. product name "Evolu", USA, Exxon Chemical (E
XXON CHEMICAL) trade name "EXACT", Dow Chemical, USA (DOW)
CHEMICAL) "Affinity- (A
FFINITY), trade name "ENGAG (ENGAG)
E) ethylene-polymerized using a metallocene catalyst such as
α-Olefin copolymer can be used.

In the present invention, for example, the back polyolefin resin layer may be formed of one of the above resins.
A resin composition is prepared by arbitrarily adding a desired additive to one or more kinds of the resin composition, and then using the resin composition prepared as described above. A film or a sheet can be formed by using a molding method such as a method of forming a back surface, and the above-mentioned back polyolefin resin layer can be formed. In the above, it is preferable that the back polyolefin-based resin layer has excellent low odor and fragrance retention properties with respect to the contents, has excellent strength and the like, and can improve stiffness and the like. In the present invention, the thickness of the back polyolefin resin layer is about 25 μm to 300 μm, and preferably about 30 μm.
A range of about μm to 200 μm is desirable.

Next, in the present invention, the vapor-deposited film of the inorganic oxide constituting the tube container packaging material, the tube container and the like according to the present invention will be described. For example, it can be formed by a chemical vapor deposition method or the like, and specifically, for example, 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. Vapor Depo
It can be formed by a method such as a position method or a CVD method. More specifically, on one surface of a resin film, a monomer gas for vapor deposition such as an organic silicon compound is used as a raw material, and an inert gas such as an argon gas or a helium gas is used as a carrier gas. A vapor-deposited film of an inorganic oxide such as silicon oxide can be formed by using a low-temperature plasma-enhanced chemical vapor deposition method using an oxygen gas or the like as an oxygen supply gas and a low-temperature plasma generator or the like. In the above description, as the low-temperature plasma generator, for example, a generator such as a high-frequency plasma, a pulse wave plasma, or a microwave plasma can be used. Thus, in the present invention, a highly active and stable plasma is obtained. For this purpose, it is desirable to use a generator using a high-frequency plasma method.

More specifically, an example of a method of forming a deposited film of an inorganic oxide by the above-described plasma enhanced chemical vapor deposition method will be described. FIG. 1 is a schematic configuration diagram of a low-temperature plasma-enhanced chemical vapor deposition apparatus showing an outline of a method for forming a deposited film of an object. As shown in FIG. 3 described above, in the present invention, the vacuum chamber-2 of the plasma enhanced chemical vapor deposition apparatus 21 is used.
The resin film 24 is unwound from an unwinding roll 23 disposed in the inside 2, and the resin film 24 is further cooled at a predetermined speed via an auxiliary roll 25.
It is transported on six peripheral surfaces. In the present invention, oxygen gas, an inert gas, a monomer gas for vapor deposition of an organic silicon compound, and the like are supplied from the gas supply devices 27 and 28 and the raw material volatilization supply device 29, and the like. While adjusting the mixed gas composition for vapor deposition, the mixed gas composition for vapor deposition was introduced into the vacuum chamber 22 through the raw material supply nozzle 30 and was transferred onto the peripheral surface of the cooling / electrode drum 26 described above. Plasma is generated by the glow discharge plasma 31 on the resin film 24, and this is irradiated to form a deposited film of an inorganic oxide such as silicon oxide, thereby forming a film. In the present invention, at this time, a predetermined power is applied to the cooling / electrode drum 26 from a power supply 32 disposed outside the chamber.
In the vicinity of 6, a magnet 33 is arranged to promote the generation of plasma, and then the resin film 24 on which the deposited film of an inorganic oxide such as silicon oxide is formed is guided to a guide roll 34 or the like. The resin film having the inorganic oxide vapor-deposited film according to the present invention can be manufactured by winding the film on a winding roll 35 or the like. In the figure, 36
Represents a vacuum pump. The above exemplification is merely an example, and it goes without saying that the present invention is not limited thereby. Although not shown, in the present invention, as a deposited film of the inorganic oxide,
Not only a single layer of the inorganic oxide deposited film but also a multilayer film in which two or more layers are laminated may be used. Also, a material to be used may be used in one kind or a mixture of two or more kinds. A vapor-deposited film of an inorganic oxide mixed with a material may be formed.

In the above, the inside of the vacuum chamber 22 is
The pressure is reduced by the empty pump 36 and the degree of vacuum is 1 × 10^-1~ 1 × 1
0^-8Torr level, preferably vacuum degree 1 × 10^-3~ 1 ×
10 ^-7It is desirable to adjust to the Torr position.
You. Further, in the raw material volatile supply device 29,
And the gas supply devices 27 and 28
Mixed with oxygen gas, inert gas, etc. supplied from
Vacuum gas through the raw material supply nozzle 30
−22. In this case, the mixed gas
The content of the organic silicon compound in the
Content is about 10-70%, inert gas content
Can be in the range of about 10-60%, for example,
The mixing ratio of organic silicon compound, oxygen gas and inert gas
The ratio can be about 1: 6: 5 to 1:17:14.
On the other hand, the cooling / electrode drum 26
Since the voltage is applied, the source in the vacuum chamber 22 is
Between the opening of the feed nozzle 30 and the cooling / electrode drum 26
Glow discharge plasma 31 is generated in the vicinity, and this glow discharge plasma 31 is generated.
The discharge plasma 31 is composed of one or more gas components in a mixed gas.
Is derived from the minute, in this state, the resin
The film 24 is transported at a constant speed, and the glow discharge
The resin on the peripheral surface of the cooling / electrode drum 26 is
Of inorganic oxide such as silicon oxide on the film 24
A film can be formed. At this time,
The degree of vacuum in the vacuum chamber is 1 × 10^-1~ 1 × 10
^-FourTorr level, preferably vacuum degree 1 × 10^-1~ 1 × 1
0^-2It is desirable to prepare at the Torr position, and the resin
The transport speed of the film 24 is about 10 to 300 m / min,
Preferably, it is desirable to adjust to 50 to 150 m / min.
It is good.

The above-mentioned plasma chemical vapor deposition apparatus 2
In (1), a vapor-deposited film of an inorganic oxide such as silicon oxide is formed on the resin film 24 in the form of a thin film in the form of SiO _X while oxidizing a plasma-converted raw material gas with oxygen gas. The formed deposited film of an inorganic oxide such as silicon oxide is a continuous layer that is dense, has few gaps, and is highly flexible. The property is much higher than that of a deposited film of an inorganic oxide such as silicon oxide formed by a conventional vacuum deposition method or the like, and a sufficient barrier property can be obtained with a thin film thickness. In the present invention,
The surface of the resin film 24 is formed by the SiO _X plasma.
Since the resin film 24 is cleaned and polar groups and free radicals are generated on the surface of the resin film 24, a film having a high adhesion between the deposited film of the inorganic oxide such as silicon oxide and the resin film is required. This has the advantage of becoming Furthermore,
As described above, the degree of vacuum at the time of forming a continuous film of an inorganic oxide such as silicon oxide is about 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, and preferably 1 × 10 ⁻¹ to 1 × 10 ^−2. Since the pressure is adjusted to the Torr level, the degree of vacuum in forming a deposited film of an inorganic oxide such as silicon oxide by a conventional vacuum deposition method is 1 × 10 ⁻⁴ to 1 ×.
Since the degree of vacuum is lower than that of 10 ^-5 Torr,
It is possible to shorten the time required to set a vacuum state when exchanging the resin film or sheet 24, so that the degree of vacuum is easily stabilized and the film forming process is stabilized.

In the present invention, a deposited silicon oxide film formed by using a vaporized monomer gas such as an organic silicon compound is chemically reacted with a vaporized monomer gas such as an organic silicon compound and oxygen gas. the reaction product is closely deposited on one surface of the resin film, dense, and forms a thin film rich in flexibility or the like, usually, the general formula SiO _X (provided that, X
Represents a number of 0 to 2), and is a continuous thin film mainly composed of silicon oxide. Thus, from the viewpoints of transparency, barrier properties, etc., the silicon oxide deposited film of the general formula Si
O _X (provided that, X represents represents. A number of 1.3 to 1.9) is intended is preferably a thin film mainly composed of vapor-deposited film of silicon oxide represented by. In the above description, the value of X changes depending on the molar ratio of the vaporized monomer gas to oxygen gas, the energy of the plasma, and the like. Is yellowish,
Transparency worsens.

The silicon oxide deposited film is mainly composed of silicon oxide, and further contains at least one compound of one or more of carbon, hydrogen, silicon or oxygen. It is characterized by being composed of a deposited film containing a kind by a chemical bond or the like. For example,
When the compound having a C—H bond, the compound having a Si—H bond, or the carbon unit is in a graphite-like, diamond-like, fullerene-like, or the like, the raw material organosilicon compound or a derivative thereof is further added. It may be contained due to chemical bonding or the like. To give a specific example, CH
Hydrocarbon with _three sites, SiH ₃ silyl, Si
Examples thereof include hydrosilica such as H ₂ silylene and hydroxyl derivative such as SiH ₂ OH silanol. In addition to the above, by changing the conditions and the like of the vapor deposition process, the type, amount, and the like of the compound contained in the vapor-deposited silicon oxide film can be changed. The content of the above compound in the silicon oxide vapor deposition film is 0.1 to 5%.
About 0%, preferably about 5 to 20% is desirable. In the above, if the content is less than 0.1%,
Impact resistance, spreadability, flexibility, etc. of the deposited film of silicon oxide become insufficient, and due to bending, scratches, cracks, etc. are easily generated, and it becomes difficult to stably maintain high barrier properties, On the other hand, if it exceeds 50%, the barrier properties are undesirably reduced. Furthermore, in the present invention, the content of the above compound in the silicon oxide vapor deposition film is preferably reduced in the depth direction from the surface of the silicon oxide vapor deposition film, whereby the silicon oxide vapor deposition film is formed. On the surface of the resin, the impact resistance and the like can be enhanced by the above-mentioned compounds, and on the other hand, at the interface with the resin film, the content of the above-mentioned compound is small, so that the resin film and the silicon oxide deposited film Has the advantage that the tight adhesion of the polymer becomes strong.

Thus, in the present invention, the above-mentioned silicon oxide vapor-deposited film is, for example, an X-ray photoelectron spectrometer (Xr
ay Photoelectron Spectros
copy, XPS), secondary ion mass spectrometer (Sec.)
onion Ion Mass Spectrosc
The above physical properties are confirmed by performing elemental analysis of a deposited silicon oxide film using a method of performing analysis by ion etching in the depth direction or the like using a surface analysis device such as O.I. can do. In the present invention, the thickness of the deposited silicon oxide film is preferably about 50 to 4000 °, and specifically, about 100 to 1000 °. Then, in the above, 1000 °, furthermore, 40
When the thickness is more than 00 °, cracks and the like are easily generated in the film, which is not preferable.
If it is less than 0 °, it is not preferable because it is difficult to exhibit the effect of the barrier property. In the above description, the film thickness can be measured by a fundamental parameter method using, for example, a fluorescent X-ray analyzer (model name: RIX2000) manufactured by Rigaku Corporation. Further, in the above, as a means for changing the thickness of the deposited film of silicon oxide, increasing the volume velocity of the deposited film, that is, a method of increasing the amount of the monomer gas and the oxygen gas or the rate of the deposition. It can be performed by a method of slowing down.

Next, in the above description, as a monomer gas for vapor deposition of an organic silicon compound or the like for forming a vapor deposition film of an inorganic oxide such as silicon oxide, for example, 1.1.3.3-tetramethyldisiloxane, Hexamethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxy Silane, phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, and the like can be used. In the present invention, among the above-mentioned organosilicon compounds, the use of 1.1.3.3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material is advantageous in handling properties and a formed continuous 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, helium gas, or the like can be used.

Next, in the present invention, the inorganic oxide vapor deposition film constituting the tube container packaging material, the tube container and the like according to the present invention may be, for example, a vacuum vapor deposition method, a sputtering method, or an ion pre-deposition method. Physical vapor deposition methods (Physical V method, such as
(apor deposition method, PVD method). In the present invention, specifically, a metal oxide is used as a raw material, and a vacuum evaporation method in which the metal oxide is heated and vapor-deposited on a resin film, or a metal or a metal oxide is used as a raw material, and oxygen is used. Oxidation reaction deposition method to introduce, oxidize and deposit on the resin film,
Further, an amorphous thin film of an inorganic oxide can be formed by using a plasma-assisted oxidation reaction deposition method in which an oxidation reaction is assisted by plasma. In the above, as a heating method of the evaporation material, for example, a resistance heating method, a high-frequency induction heating method, an electron beam heating method (EB), or the like can be used.

In the present invention, as the above-mentioned inorganic oxide vapor-deposited film, basically, any thin film on which a metal oxide is vapor-deposited can be used.
i), aluminum (Al), magnesium (Mg),
Calcium (Ca), potassium (K), tin (Sn),
Sodium (Na), boron (B), titanium (Ti),
A vapor-deposited film of an oxide of a metal such as lead (Pb), zirconium (Zr), or yttrium (Y) can be used. Thus, preferred are silicon (Si),
An evaporation film of a metal oxide such as aluminum (Al) can be given. Thus, the above-mentioned vapor-deposited film of a metal oxide can be referred to as a metal oxide, such as silicon oxide, aluminum oxide, and magnesium oxide. The notation is, for example, SiO _x , AlO _x , MO _X (However, as such MgO _X, wherein, M represents a metal element,
The range of the value of X differs depending on the metal element. )
It is represented by The range of the value of X is 0 to 2 for silicon (Si) and 0 to 2 for aluminum (Al).
1.5, magnesium (Mg) is 0-1, calcium (Ca) is 0, potassium (K) is 0-0.5,
Tin (Sn) is 0-2, and sodium (Na) is 0-2.
0.5, boron (B) is 0-1,5, titanium (Ti)
Is 0-2, lead (Pb) is 0-1, zirconium (Z
r) 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, it is not transparent and cannot be used at all, and the upper limit of the range of X is a completely oxidized value. In the present invention, generally, silicon (S
i), except for aluminum (Al), few examples are used. Silicon (Si) has a value in the range of 1.0 to 2.0, and aluminum (Al) has a value in the range of 0.5 to 1.5. Can be used. In the present invention, the thickness of the inorganic oxide deposited film as described above, depending on the type of metal used, or metal oxide, etc., for example,
About 50-4000 °, preferably 100-1000 °
It is desirable to arbitrarily select and form within the range of the order.
In the present invention, the metal to be used as the inorganic oxide deposited film or the metal oxide is 1
It is also possible to use a mixture of two or more of these species to form a vapor-deposited film of an inorganic oxide mixed with different materials.

Next, in the present invention, a specific example of a method of forming the above-mentioned vapor-deposited film of an inorganic oxide will be described. FIG. 4 is a schematic configuration diagram showing an example of a roll-up type vacuum vapor deposition apparatus. . As shown in FIG. 4, the unwinding roll is placed in a vacuum chamber 42 of a take-up type vacuum evaporation apparatus 41.
The resin film 44 fed out of the guide 43
Cooled coating drum 4 via
Guided to 7. Thus, on the resin film 44 guided on the cooled coating drum 47,
The evaporation source 49 heated in the crucible 48, for example, metal aluminum or aluminum oxide is evaporated,
Further, if necessary, while jetting oxygen gas or the like from the oxygen gas outlet 50, for example, through the masks 51, 51,
This is for forming a deposited film of an inorganic oxide such as aluminum oxide. Next, in the present invention, for example, the guide rolls 52, 5
The film can be wound around a winding roll 54 or the like via 3 or the like to produce a resin film having a vapor-deposited inorganic oxide film according to the present invention. The above exemplification is merely an example, and it goes without saying that the present invention is not limited thereby. In the present invention, first, a first-layer inorganic oxide vapor-deposited film is formed using the above-mentioned winding vacuum vapor deposition apparatus, and then, similarly, the inorganic oxide vapor-deposited film is formed. On top of this, an inorganic oxide vapor deposition film is further formed, or by using a roll-up vacuum vapor deposition device as described above, this is connected in series, and the inorganic oxide vapor deposition is continuously performed. By forming the film, an inorganic oxide vapor-deposited film including a multilayer film of two or more layers can be formed.

Next, in the present invention, the resin film constituting the resin film provided with the above-mentioned inorganic oxide vapor-deposited film has excellent chemical or physical strength,
The base material can be used because it can withstand the conditions for forming an inorganic oxide vapor-deposited film and the like and can favorably retain the properties of the inorganic oxide vapor-deposited film and the like without being impaired. In the present invention, as the resin film, specifically, for example, a polyolefin resin such as a polyethylene resin or a polypropylene resin, a cyclic polyolefin resin, a polystyrene resin, an acrylonitrile-styrene copolymer (AS resin) ), Acrylonitrile-butadiene-styrene copolymer (ABS resin), poly (meth) acrylic resin, polycarbonate resin, polyester resin such as polyethylene terephthalate, polyethylene naphthalate, etc. Films or sheets of various resins such as polyamide resin such as nylon, polyurethane resin, acetal resin, cellulose resin and others can be used. In the present invention, among the above resin films or sheets, it is particularly preferable to use a polyester resin, a polyolefin resin, or a polyamide resin film or sheet.

In the present invention, as the film or sheet of the above-mentioned various resins, for example, one or more of the above-mentioned various resins are used, and are extruded, cast-formed, T-die-processed, and cut. A method of forming the above various resins alone using a film forming method such as an inflation method, an inflation method, or the like, or a multi-layer coextrusion film forming using two or more kinds of resins. A film or a sheet of various resins is manufactured by a method of forming two or more resins, and a method of mixing and forming a film before forming a film. For example, various resin films or sheets stretched in a uniaxial or biaxial direction using a tenter method or a tuber method can be used. In the present invention, the film thickness of various resin films or sheets is 6 to 200 μm.
And more preferably about 9 to 100 μm.

When one or more of the various resins described above are used and the film is formed, for example, the processability, heat resistance, weather resistance, mechanical properties, dimensional stability,
It is possible to add various plastic additives and additives for the purpose of improving or modifying the antioxidant properties, slip properties, mold release properties, flame retardancy, anti-mold properties, electrical properties, strength, etc. Can,
The addition amount can be arbitrarily added from a very small amount to several tens% depending on the purpose. In the above, as a general additive, for example, a lubricant, a crosslinking agent,
An antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a pigment, and the like can be used, and further, a modifying resin and the like can be used.

In the present invention, the surface of the film or sheet of various resins may have a desired surface in advance, if necessary, in order to improve the tight adhesion with the inorganic oxide vapor-deposited film. A treatment layer can be provided. In the present invention, as the surface treatment layer, for example, corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using a chemical, etc., Pretreatment such as others can be arbitrarily performed, and for example, a corona treatment layer, an ozone treatment layer, a plasma treatment layer, an oxidation treatment layer, and the like can be formed and provided. The above-mentioned surface pretreatment is carried out as a method for improving the tight adhesion between the film or sheet of various resins and the deposited film of the inorganic oxide. In addition, for example, a primer coat agent layer, an undercoat agent layer, an anchor coat agent layer, an adhesive layer may be previously formed on the surface of various resin films or sheets. Alternatively, a surface-treated layer can be formed by arbitrarily forming a vapor-deposited anchor coating agent layer or the like. Examples of the coating agent layer in the above pretreatment include polyester resin, polyamide resin, polyurethane resin, epoxy resin, phenol resin, (meth) acrylic resin, polyvinyl acetate resin, A resin composition containing, as a main component of the vehicle, a polyolefin resin such as polyethylene aliha polypropylene or a copolymer or modified resin thereof, a cellulose resin, or the like can be used.

Next, in the present invention, a resin film provided with a surface polyolefin-based resin layer and a vapor-deposited film of an inorganic oxide, or a resin film provided with a vapor-deposited film of an inorganic oxide and a back polyolefin-based resin layer As a method of laminating, for example, a dry laminating method of laminating via a primer agent layer and a laminating adhesive layer, or
Lamination can be performed by a melt extrusion laminating method or the like in which lamination is performed via a primer agent layer and a melt extruded resin layer.

In the above, as the primer agent layer,
First, a polyurethane-based resin is used as a main component of the vehicle, and a silane coupling agent is used in an amount of about 0.05 to 10% by weight, preferably 0.1 to 30% by weight, based on 1 to 30% by weight of the polyurethane-based resin.
1 wt% to 5 wt%, filler 0.1 to 20 wt%,
Preferably, it is added at a ratio of about 1 to 10% by weight,
If necessary, add additives such as stabilizers, curing agents, cross-linking agents, lubricants, ultraviolet absorbers, etc., add solvents, diluents, etc. and mix well to adjust the polyurethane resin composition Thus, the polyurethane-based resin composition is used, for example, roll coat, gravure coat,
The above-mentioned inorganic oxide vapor-deposited film is coated by knife coating, dip coating, spray coating, or another coating method, and then the coating film is dried to form a solvent, The diluent and the like can be removed, and if necessary, an aging treatment or the like can be performed to form the primer agent layer according to the present invention. In the present invention, the thickness of the primer agent layer is, for example, 0.1 g / m ^2.
It is preferably about 1.0 g / m ² (dry state). Thus,
In the present invention, the above-mentioned primer agent layer improves the close adhesiveness and the like and the elongation degree of the primer agent layer by, for example, laminating or bag forming. It is intended to improve workability and prevent the occurrence of cracks and the like in the deposited film of the inorganic oxide during post-processing.

In the above description, as the polyurethane resin constituting the polyurethane resin composition, for example, a polyurethane resin obtained by reacting a polyfunctional isocyanate with a hydroxyl group-containing compound can be used. Specifically, for example, tolylene diisocyanate-
Aromatic polyisocyanate such as diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, or hexamethylene diisocyanate
And polyfunctional isocyanates such as aliphatic polyisocyanates such as xylylene diisocyanate and hydroxyl group-containing compounds such as polyether polyols, polyester polyols, polyacrylate polyols and the like. One- or two-component curable polyurethane resins obtained by the reaction can be used. Thus, in the present invention, the use of the above-mentioned polyurethane-based resin improves the close-adhesion property and the like and improves the primer property.
It improves the elongation of the agent layer, for example, laminating, or improving post-processing suitability such as bag making, and prevents the occurrence of cracks and the like in the inorganic oxide deposited film during post-processing. is there.

Next, in the above, as the silane coupling agent constituting the polyurethane resin composition,
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, aqueous solution of γ-aminopropylsilicone, etc. Seeds or more 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). , A metal constituting the deposited film of the inorganic oxide, or an active group on the surface of the deposited film of the inorganic oxide, for example, by any action with a functional group such as a hydroxyl group, for example, causing a reaction such as a dehydration condensation reaction. The silane coupling agent is modified by a covalent bond or the like on the surface of the deposited inorganic oxide film, and a strong bond is formed on the surface of the deposited inorganic oxide film of the silanol group itself by adsorption or hydrogen bonding. . On the other hand, the other end of the silane coupling agent vinyl, methacryloxy, amino, epoxy, or
An organic functional group such as mercapto is formed on a thin film of the silane coupling agent, for example, reacts with a material constituting an adhesive layer for lamination, a melt-extruded resin layer, other layers, etc., and becomes strong. A strong bond is formed through the adhesive layer for laminating, the melt-extruded resin layer, etc., and the laminating strength is increased. Is to form a strong laminated structure having high laminate strength. In the present invention, utilizing the inorganic and organic properties of the silane coupling agent,
Improving the tight adhesion between the front or back surface polyolefin resin layer through the inorganic oxide deposited film, the laminating adhesive layer, the melt-extruded resin layer, etc., thereby increasing the laminating strength, etc. Is to increase.

Next, in the present invention, examples of the filler constituting the polyurethane resin composition include calcium carbonate, barium sulfate, alumina white, silica, talc, glass frit, resin powder, and the like. Can be used. Thus, the above filler is
The viscosity and the like of the polyurethane resin composition liquid are adjusted to improve the coating suitability, and the polyurethane resin as a binder resin is bonded via a silane coupling agent to improve the cohesive force of the coating film. It is to let.

Next, in the present invention, examples of the laminating adhesive constituting the laminating adhesive layer include a polyvinyl acetate adhesive, ethyl acrylate, and the like.
Homopolymers such as butyl and 2-ethylhexyl esters, or polyacrylate adhesives, cyanoacrylate adhesives composed of copolymers of these with methyl methacrylate, acrylonitrile, styrene, etc., ethylene and vinyl acetate Ethylene copolymer adhesive, cellulose adhesive, polyester adhesive, polyamide adhesive, polyimide adhesive consisting of copolymers with monomers such as ethyl acrylate, acrylic acid, methacrylic acid, etc. , Urea resin or melamine resin, amino resin adhesive, phenol resin adhesive, epoxy adhesive, polyurethane adhesive, reactive (meth) acrylic adhesive, chloroprene rubber, nitrile rubber, styrene -Rubber adhesives composed of butadiene rubber, etc., silicone-
Inorganic adhesives, such as inorganic adhesives, alkali metal silicates, low-melting glass, etc., and other adhesives can be used. The composition system of the above-mentioned adhesive may be any composition form such as an aqueous type, a solution type, an emulsion type, and a dispersion type, and the properties thereof include a film sheet, a powder, and a solid. Any form may be used, and the bonding mechanism may be any form such as a chemical reaction type, a solvent volatilization type, a heat melting type, and a heat pressure type. Thus, in the present invention, the laminating adhesive is applied to one surface of both layers to be laminated, for example, by a roll coat method, a gravure roll coat method, a kiss coat method, or the like. Coating method such as
Alternatively, the adhesive may be applied by a printing method or the like, and then a solvent or the like may be dried to form an adhesive layer for laminating.
/ M ² (dry state).

In the present invention, examples of the melt-extruded resin constituting the above-mentioned melt-extruded resin layer include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, and metallocene. Ethylene-α-olefin copolymer, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene- Methacrylic acid copolymer, ethylene-propylene copolymer,
Use an acid-modified polyolefin resin obtained by modifying a polyolefin resin such as methylpentene polymer, polyethylene, or polypropylene with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, or the like, or the like. be able to. Further, in the present invention, when the melt extrusion lamination, isocyanate system,
Anchor coating agents such as polyethyleneimine and others can be arbitrarily used. Furthermore, in the present invention, when performing the above-mentioned lamination, if necessary, for example, a pretreatment such as a corona treatment, an ozone treatment, or a framing treatment is optionally performed on the surface of the base material to be laminated. be able to.

Usually, packaging containers are subjected to severe physical and chemical conditions, so that the laminate material constituting the packaging containers is required to have strict packaging suitability.
Various conditions such as deformation prevention strength, drop impact strength, pinhole resistance, heat resistance, sealing property, quality maintenance, workability, hygiene, etc. are required. For this reason, in the present invention, In addition to such materials, other materials that satisfy the above conditions can be used arbitrarily. 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, methylpentene 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 Coalesce (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin, polycarbonate resin, polyvinyl alcohol
Resin, ethylene-vinyl acetate copolymer saponified product,
Fluorine resin, diene resin, polyacetal resin,
A film or sheet of a known resin such as a polyurethane resin, nitrocellulose, or the like can be arbitrarily selected and used. In addition, for example, synthetic paper can be used. In the present invention, the above-mentioned film or sheet can be used in any of unstretched and uniaxially or biaxially stretched. The thickness is arbitrary, but is from several μm to 300 μm.
It can be used by selecting from a range of positions. 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.

Further, in the present invention, the other base material has excellent properties in mechanical, physical, chemical, etc. as a basic material constituting a laminating tube container, for example. In particular, a resin film or sheet having strength, toughness, and heat resistance can be used. Specifically, for example, polyester resin, polyamide resin, polyaramid resin,
Films or sheets of tough resins such as polyolefin resins, polycarbonate resins, polyacetal resins, fluorine resins, and others can be used. As the resin film or sheet, any of an unstretched film and a stretched film stretched in a uniaxial or biaxial direction can be used. The thickness of the film is 5μ
m to 100 μm, preferably 10 μm to 5 μm
About 0 μm is desirable.

In the present invention, examples of the barrier material or the material having a scent-retaining property include polyvinylidene chloride resin, polyester resin, MXD
Polyamide resin, ethylene-vinyl acetate copolymer (vinyl acetate is about 79-92 wt%), ethylene-vinyl alcohol copolymer having an ethylene content of 25-50 mol%, polyvinyl alcohol, poly A resin film or sheet having a high gas barrier property such as acrylonitrile or the like, or a coating film can be used. Further, in the present invention, as other materials, for example, a light-shielding material having a property of blocking light such as sunlight, or a water-resistant material having a property of not transmitting water vapor, water, or the like is used. This may be a single base material or a composite base material obtained by combining two or more types of base materials. Specifically, for example, water-resistant materials having barrier properties such as water vapor and water include, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, and ethylene-propylene. A resin film or sheet of a polymer or the like can be used, and as a light-shielding material, for example, a coloring agent such as a pigment is added to a resin, and further, a desired additive such as other is added and kneaded. Various colored resin films or sheets having a light-shielding property and formed into a film can be used.
These materials can be used alone or in combination of two or more. The thickness of the above-mentioned film or sheet is arbitrary, but is usually 5 μm to 300 μm.
μm, more preferably about 10 μm to 100 μm.

In the present invention, the method for producing the tube container packaging material according to the present invention using the above-mentioned materials will be described.
Lamination methods used when manufacturing ordinary packaging materials, for example, wet lamination method, dry lamination method, solventless dry lamination method, extrusion lamination method, T-die co-extrusion molding method, It can be carried out by any method such as a co-extrusion lamination method, an inflation method and others. Thus, in the present invention, when performing the above lamination, if necessary, a pretreatment such as a corona treatment or an ozone treatment can be applied to the film. (Urethane-based), polyethyleneimine-based, polybutadiene-based, organic titanium-based anchor coating agents, or polyurethane-based, polyacryl-based, polyester-based,
Known anchor coating agents such as epoxy-based, polyvinyl acetate-based, cellulose-based, and other laminating adhesives;
An adhesive for laminating or the like can be optionally used.
Further, in the present invention, any of the substrates constituting the tube container packaging material according to the present invention, before lamination, for example, gravure printing method, offset printing method, letterpress printing method, A desired printing pattern can be formed by using a silk screen printing method, a flexographic printing method, or the like. Specifically, in the present invention, a desired printed pattern or the like can be formed on a substrate constituting the surface polyolefin-based resin layer, or a resin film having a vapor-deposited film of an inorganic oxide. .

Next, in the present invention, when manufacturing the tube container according to the present invention, for example, as a method of heat sealing when manufacturing the cylindrical body portion, for example, a base seal is used. It can be performed by a known method such as a roll seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, an ultrasonic seal, a flame seal, or the like.

Next, in the present invention, the tube container wrapping material produced as described above is used. First, the surface of the tube container wrapping material is applied by a gravure printing method, a flexo printing method, or the like. Using gravure ink, flexo ink, etc., print and form a print pattern layer composed of characters, figures, symbols, pictures, etc., and then roll up the tube container packaging material on which the print pattern layer is formed The polymerized end is welded to produce a cylindrical body constituting a tube container, and then, for example, a high-density polyethylene or the like is injected above the cylindrical body by injection molding, compression molding, or the like. Forming and welding by other molding methods to form a head including a shoulder and a mouth, and then separately forming, for example, an injection molding method using a polypropylene resin or the like in a mouth constituting the head. Attach the cap manufactured by molding with It is possible to produce a blanking container - according Ju. Therefore, in the present invention, the contents to be filled and packed are filled through the opening at the lower end of the tube container manufactured as described above, and then the opening is heat-sealed to form a bottom welded portion. Thus, a packaged product comprising the tube container according to the present invention can be manufactured. In the above, the contents to be filled and packaged include, for example, toothpaste, cosmetics, glue, paste, paste wasabi, creams, paints, ointments, medicines, and the like. In the above, in addition to the above-described high-density polyethylene, the above-described metallocene catalyst is used as a material for forming the head portion of the tube container according to the present invention including the shoulder portion and the mouth portion. Ethylene-α-olefin copolymers and the like can also be used.

In the above description, flexographic printing is a type of letterpress printing, in which a flexible resin or rubber letterpress is used, and a solvent-drying type flexographic ink is used to form letters, figures, symbols, pictures, and other patterns. The desired printed pattern layer is formed by printing. In addition, as the above-mentioned flexo ink, an evaporative drying ink mainly containing an alcohol or water-based vehicle, which does not relatively invade a rubber letterpress or the like, or an ultraviolet curable ink can be used. is there. Thus, in the present invention, a tube container packaging material is manufactured in a plain state by using a flexographic printing method or the like, and the plain tube is manufactured.
Since it can be printed directly on the surface of the packaging material for the container or the plain cylindrical part, the desired printed pattern layer can be formed,
Batch production of raw materials becomes possible, increasing the production efficiency,
It is possible to reduce production loss, etc.
Short delivery time is possible. That is, usually, a desired printing pattern layer is formed by printing on an original film such as a plastic film, and thereafter, another plastic film or the like is laminated thereon to produce a laminated material with a printing pattern. As a result, the lead time from receiving orders becomes longer, and the raw material lot is identified for each pattern.
Although the manufacturing cost is significantly disadvantageous, the present invention has an advantage that such a problem can be solved.

[0045]

EXAMPLES Next, the present invention will be described more specifically with reference to examples. Example 1 (1). A biaxially stretched nylon 6 film having a thickness of 15 μm was used, and was mounted on a delivery roll of a plasma-enhanced chemical vapor deposition apparatus. Then, a deposited film of silicon oxide having a thickness of 200 ° was formed. (Evaporation conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1.2: 5.0: 2.5 (unit: sl)
m) Ultimate pressure; 5.0 × 10 ⁻⁵ mbar Film forming pressure; 7.0 × 10 ⁻² mbar Line speed; 300 m / min Power; 35 kW Next, a silicon oxide vapor deposition film having a thickness of 200 ° Immediately after the formation, on the surface of the deposited silicon oxide film, using a glow discharge plasma generator, power: 9 kW, oxygen gas (O ₂ ): argon gas (Ar) = 7.0: 2.5 (unit) : Slm) and a mixed gas pressure of 6
× 10 ^-2 mbar, oxygen /
An argon mixed gas plasma treatment was performed to form a plasma treatment surface in which the surface tension of the silicon oxide deposited film surface was improved by 54 dyne / cm or more, thereby producing a barrier film according to the present invention. (2). Next, an epoxy-based silane coupling agent (8.0% by weight) and an anti-blocking agent ( 1.0% by weight) and sufficiently kneaded, and a gravure roll coat method is used to obtain a primer composition having a thickness of 0.4 g / m ² (dry state). Then, a primer agent layer was formed. Next, on the primer agent layer, using a normal gravure ink composition, by a gravure printing method, printing a predetermined print pattern consisting of characters, figures, symbols, patterns, etc. Was formed. Next, a two-component curable polyurethane-based laminating adhesive was used on the entire surface including the printed pattern layer formed above, and this was applied to a film thickness of 4.0 g / m 2 by a gravure roll coating method. ² Make sure that it is dry (dry).
To form a laminate adhesive layer. Next, the thickness of the laminating adhesive layer formed on the
A 70 μm low-density polyethylene film was overlaid with its corona-treated surface facing each other, and then both were laminated by dry lamination. On the other hand, a two-component curable polyurethane-based laminating adhesive was used on the entire surface of a low-density polyethylene film having a thickness of 170 μm, and this was applied to a film thickness of 4.0 g / m ² by a gravure roll coating method. (Laminated state) to form an adhesive layer for lamination. Next, a barrier film obtained by laminating a low-density polyethylene film having a thickness of 170 μm above on the surface of the adhesive layer for laminating formed above is laminated with the surface of the biaxially stretched nylon 6 film facing the same. Thereafter, both were dry-laminated to produce a packaging material for a tube container according to the present invention. (3). Next, using the tube container packaging material produced above, first, the tube container packaging material was punched to produce a blank plate, and then the blank plate was rolled up.
3 Kg of the back end of the superposed end at 215 ° C. for 3 seconds
Heat sealing under heat welding conditions of 35 m / cm ² and a diameter of 35 m.
m, a cylindrical body serving as a body of a tube container having a height of 160 mm was produced. Next, the above-prepared cylindrical body is mounted on a mandrel for forming a tube container, and then, at one end of the cylindrical body, a frusto-conical shoulder portion and a continuous narrow neck opening are formed in a conventional manner. The head consisting of the neck is made of high-density polyethylene 9
A high-density polyethylene composition in which 2.0% by weight of an opalescent pigment was added to 8.0 parts by weight was molded at a resin temperature of 245 ° C. by a compression molding method to produce a tube container according to the present invention. . Next, on the mouth and neck of the cylindrical body having the above head,
A cap made of a polypropylene resin is spirally wound, and then the other opening of the cylindrical body is filled with 150 g of kneaded wasabi, and then the opening of the cylindrical body is heat-sealed to form a tube container. Manufactured packaging products. The packaged product comprising the tube container manufactured as described above is excellent in barrier properties against oxygen gas, water vapor, etc., is excellent in laminate strength, etc., withstands distribution in the market, and is excellent in storage and storage. Was something. . There was no particular problem even if the used tube container and the like were incinerated and disposed of.

Embodiment 2 (1). As a base film, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used.
The above biaxially stretched polyethylene terephthalate film was mounted on a delivery roll of a plasma chemical vapor deposition apparatus, and then unwound, and the following vapor deposition was performed on the corona-treated surface of the biaxially stretched polyethylene terephthalate film. Under the conditions, a deposited film of silicon oxide having a thickness of 200 ° was formed. (Evaporation conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 11: 10 (unit: slm) Degree of vacuum in vacuum chamber: 5.2 × 10 ⁻⁶ mbar In evaporation chamber Degree of vacuum: 5.1 × 10 ^-2 mbar Cooling / electrode drum supply power: 60 w / min / m ² Film transport speed: 90 m / min Vapor deposition surface: corona treated surface Immediately after the deposition film was formed, the surface of the silicon oxide film was deposited on the surface of the silicon oxide film.
In the same manner as described above, plasma treatment was performed to form a plasma-treated surface in which the surface tension of the silicon oxide deposited film surface was improved by 54 dyne / cm or more, thereby producing a barrier film according to the present invention. (2). On the other hand, a two-part curable polyurethane-based laminating adhesive was used on one entire surface of a low-density polyethylene film having a thickness of 170 μm, and this was applied to a film thickness of 4.0 g / g by a gravure roll coating method. m ² (dry state) to form an adhesive layer for lamination. Next, the barrier film produced in the above (1) is superimposed on the surface of the laminating adhesive layer formed above with the surface of the biaxially stretched polyethylene terephthalate film facing the substrate. And both were dry-laminated. Next, on the plasma-treated surface of the silicon oxide vapor-deposited film of the dry-laminated barrier film, a polyurethane-based initial condensate, an epoxy-based silane coupling agent (8.0% by weight) and blocking prevention were applied. (1.0% by weight), and kneaded well to use a primer composition, which is gravure roll coated to a film thickness of 0.4 g / m ² (dry state). Thus, a primer agent layer was formed by coating. Further, a two-component curable polyurethane-based laminating adhesive is used on the entire surface including the primer agent layer formed as described above, and the adhesive is applied by a gravure roll coating method in the same manner as described above. An adhesive layer for lamination was formed by coating so as to be 4.0 g / m ² (dry state). Next, a 170 μm thick layer was formed on the surface of the laminating adhesive layer formed above.
Were laminated with their corona-treated surfaces facing each other, and then both were dry-laminated. Furthermore, on the surface of the low-density polyethylene film having a thickness of 170 μm as the surface polyolefin-based resin layer, after corona discharge treatment, the corona-treated surface, using an ultraviolet curable flexographic ink composition, by flexographic printing method, A desired printed picture layer was formed to produce a tube container packaging material according to the present invention. (3). Next, using the above-prepared packaging material for a tube container, in the same manner as in Example 1 above, first, a cylindrical body serving as the body of the tube container was manufactured. At one end, a head consisting of a frustoconical shoulder and a continuous neck and neck was formed by compression molding to produce a tube container according to the present invention. Next, a cap made of polypropylene resin is spirally wound around the mouth and neck of the cylindrical body having the above-mentioned head, and then, from the other opening of the cylindrical body, 150 g of a chocolate whip cream is filled. The opening of the cylindrical body was heat-sealed to produce a packaged product comprising a tube container. The packaged product comprising the tube container manufactured as described above is excellent in barrier properties against oxygen gas, water vapor, etc., is excellent in laminate strength, etc., withstands distribution in the market, and is excellent in storage and storage. Was something. . There was no particular problem even if the used tube container and the like were incinerated and disposed of.

Embodiment 3 (1). As a base film, a biaxially stretched nylon 6 film having a thickness of 15 μm was used. First, the above biaxially stretched nylon 6 film was mounted on a delivery roll of a take-up type vacuum evaporation apparatus, and then this was rolled. The aluminum is used as a vapor deposition source and oxygen gas is supplied to the corona-treated surface of the biaxially stretched nylon 6 film, and a vacuum vapor deposition method using an electron beam (EB) heating method is used under the following vapor deposition conditions. Then, a deposited film of aluminum oxide having a thickness of 200 ° was formed. (Evaporation conditions) Degree of vacuum in evaporation chamber: 2 × 10 ⁻⁴ mbar Degree of vacuum in winding chamber: 2 × 10 ⁻² mbar Electron beam power: 25 kW Film transport speed: 240 m / min Evaporation surface : Corona-treated surface Next, immediately after forming the above-described 200-mm-thick aluminum oxide vapor-deposited film, a plasma-treated surface was formed on the aluminum oxide-deposited film in the same manner as in Example 1 above. A barrier film according to the present invention was produced. (2). On the other hand, a low-density polyethylene film having a thickness of 170 μm was used, and a printed pattern layer was formed on one surface thereof in the same manner as in Example 1 above.
m, a laminating adhesive layer is formed on the other entire surface of the low-density polyethylene film, and the barrier film produced in the above (1) is further formed on the laminating adhesive layer. The biaxially stretched nylon 6 films were superposed on each other with their surfaces facing each other, and then both were dry-laminated. Next, a primer agent layer was formed on the plasma-treated surface of the vapor-deposited aluminum oxide film of the barrier film dried as described above in the same manner as in Example 1 above.
Further, an adhesive layer for laminating was formed on the entire surface including the primer agent layer formed above. Next, a low-density polyethylene film having a thickness of 170 μm is laminated on the laminating adhesive layer surface formed above with the corona-treated surface facing the film, and then both are dry-laminated. A packaging material for a tube container according to the invention was manufactured. (3). Next, using the above-prepared packaging material for a tube container, in the same manner as in Example 1 above, first, a cylindrical body serving as the body of the tube container was manufactured. At one end, a head consisting of a frustoconical shoulder and a continuous neck and neck was formed by compression molding to produce a tube container according to the present invention. Next, a cap made of a polypropylene resin is spirally wound around the mouth and neck of the cylindrical body having the above-mentioned head, and then, from the other opening of the cylindrical body, 150 g of kneaded wasabi is filled. The opening was heat-sealed to produce a packaged product consisting of a tube container. The packaged product comprising the tube container manufactured as described above is excellent in barrier properties against oxygen gas, water vapor, etc., is excellent in laminate strength, etc., withstands distribution in the market, and is excellent in storage and storage. Was something. . There was no particular problem even if the used tube container and the like were incinerated and disposed of.

Embodiment 4 (1). As a base film, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used.
The above-mentioned biaxially stretched polyethylene terephthalate film was mounted on a delivery roll of a take-up type vacuum evaporation apparatus, and then unwound. The corona-treated surface of the biaxially stretched polyethylene terephthalate film was coated with aluminum. Was used as a vapor deposition source while supplying oxygen gas to form a 200-Å-thick aluminum oxide vapor-deposited film by a vacuum vapor deposition method using an electron beam (EB) heating method under the following vapor deposition conditions. (Evaporation conditions) Degree of vacuum in evaporation chamber: 2 × 10 ⁻⁴ mbar Degree of vacuum in winding chamber: 2 × 10 ⁻² mbar Electron beam power: 25 kW Film transport speed: 240 m / min Evaporation surface : Corona-treated surface Next, immediately after forming the above-described 200-mm-thick aluminum oxide vapor-deposited film, a plasma-treated surface was formed on the aluminum oxide-deposited film in the same manner as in Example 1 above. A barrier film according to the present invention was produced. (2). On the other hand, a two-part curable polyurethane-based laminating adhesive was used on one entire surface of a low-density polyethylene film having a thickness of 170 μm, and this was applied to a film thickness of 4.0 g / g by a gravure roll coating method. m ² (dry state) to form an adhesive layer for lamination. Next, the barrier film produced in the above (1) is superimposed on the surface of the laminating adhesive layer formed above with the surface of the biaxially stretched polyethylene terephthalate film facing the substrate. And both were dry-laminated. Next, on the plasma-treated surface of the silicon oxide vapor-deposited film of the dry-laminated barrier film, a polyurethane-based initial condensate, an epoxy-based silane coupling agent (8.0% by weight) and blocking prevention were applied. (1.0% by weight), and kneaded well to use a primer composition, which is gravure roll coated to a film thickness of 0.4 g / m ² (dry state). Thus, a primer agent layer was formed by coating. Further, a two-component curable polyurethane-based laminating adhesive is used on the entire surface including the primer agent layer formed as described above, and the adhesive is applied by a gravure roll coating method in the same manner as described above. An adhesive layer for lamination was formed by coating so as to be 4.0 g / m ² (dry state). Next, a 170 μm thick layer was formed on the surface of the laminating adhesive layer formed above.
Were laminated with their corona-treated surfaces facing each other, and then both were dry-laminated. Furthermore, on the surface of the low-density polyethylene film having a thickness of 170 μm as the surface polyolefin-based resin layer, after corona discharge treatment, the corona-treated surface, using an ultraviolet curable flexographic ink composition, by flexographic printing method, A desired printed picture layer was formed to produce a tube container packaging material according to the present invention. (3). Next, using the above-prepared packaging material for a tube container, in the same manner as in Example 1 above, first, a cylindrical body serving as the body of the tube container was manufactured. At one end, a head consisting of a frustoconical shoulder and a continuous neck and neck was formed by compression molding to produce a tube container according to the present invention. Next, a cap made of polypropylene resin is spirally wound around the mouth and neck of the cylindrical body having the above-mentioned head, and then, from the other opening of the cylindrical body, 150 g of a chocolate whip cream is filled. The opening of the cylindrical body was heat-sealed to produce a packaged product comprising a tube container. The packaged product comprising the tube container manufactured as described above is excellent in barrier properties against oxygen gas, water vapor, etc., is excellent in laminate strength, etc., withstands distribution in the market, and is excellent in storage and storage. Was something. . There was no particular problem even if the used tube container and the like were incinerated and disposed of.

Experimental Examples The packaging materials for tube containers produced in Examples 1 to 4 were measured for oxygen permeability, water vapor permeability, puncture resistance, and storage suitability. (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 transmission rate This is a condition of temperature of 40 ° C and humidity of 90% RH in the United States,
The measurement was carried out using a measuring instrument (model name, PERMATRAN) manufactured by MOCON. (3). Measurement of Seal Strength In this test, a tensile strength tester was used to measure the seal strength of the trunk, end seal, and shoulder seal. The above measurement results are shown in Table 1 below.

[0050] In Table 1 above, the unit of oxygen permeability is [cc / m
² / day · 23 ° C. · 90% RH] and the unit of water vapor permeability is [g / m ² / day · 40 ° C. · 10
0% RH], and the unit of the seal strength is [kg / 15
mm].

As is clear from the measurement results shown in Table 1 above, the packaging material for a tube container according to the present invention has excellent oxygen barrier properties and water vapor barrier properties, and has a high seal strength. Was also excellent, and could sufficiently withstand use as a tube container for filling and packaging foods and drinks.

[0052]

As is clear from the above description, the present invention
As a barrier material, silicon oxide, attention is paid to a barrier film composed of a resin film provided with a vapor-deposited film of an inorganic oxide such as aluminum oxide, and further, attention is paid to using the barrier film inside, At least the surface polyolefin-based resin layer, the above-mentioned barrier film, and the back surface polyolefin-based resin layer are sequentially laminated to produce a tube container packaging material, and thus the tube container packaging material. And the surface of the outermost polyolefin resin layer as the outermost layer at both ends of the tube container packaging material and the surface of the lowermost polyolefin resin layer as the innermost layer are overlapped. A tubular body is formed by sealing, and a head including a shoulder and a mouth is provided at one opening of the tubular body, and a cap is screwed into the head to form a tube. -Manufacture the container, and Ju - filling the contents from the other opening of the cylindrical body constituting the blanking container, thereafter, the opening sealing sheet - bottom sheet and Le - forming a pole tip, Ju -
Manufacture of packaging products made of cubic containers, having strength, etc., and having excellent heat resistance, moisture resistance, heat sealability, pinhole resistance, piercing resistance, transparency, etc. Oxygen gas,
It has excellent barrier properties to prevent the permeation of water vapor, etc., has suitability for filling and preserving its contents, and also has suitability for preservation. Suitable for disposal without generating harmful substances,
It is possible to produce a tube container wrapping material which is extremely excellent in environmental suitability and the like and a tube container using the same.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing an example of a layer structure of a tube container packaging material according to the present invention.

FIG. 2 is a schematic half sectional view showing the configuration of a tube container according to the present invention manufactured using the tube container packaging material according to the present invention shown in FIG.

FIG. 3 is a schematic configuration diagram illustrating an example of a low-temperature plasma chemical vapor deposition apparatus.

FIG. 4 is a schematic configuration diagram illustrating an example of a take-up type vacuum evaporation apparatus.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Surface polyolefin resin layer 2 Inorganic oxide vapor deposition film 3 Resin film 1a Back polyolefin resin layer 11 Welded part 12 Cylindrical trunk part 13 Shoulder part 14 Port part 15 Head 16 Cap 17 Contents 18 Bottom weld part A Tube container packaging material R Tube container Ra Packaging product

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C23C 14/08 C23C 14/08 A 4K030 14/20 14/20 A 16/40 16/40 F term (reference) 3E065 AA01 BA15 BA16 BA17 BA18 BA26 BA28 BA30 BA34 BB03 CA09 DA04 DB05 DC01 DD05 EA04 FA15 FA20 GA01 GA03 GA10 HA10 3E067 AA04 AB01 AB21 AB26 AB81 AB99 BA14A BB11A BB12A BB14A BB15A BB16A BB25 CA04 CA05 CA04 CA05 CA04 CA05 BB62 CA01 CA28 CA35 DA08 4F100 AA00C AA19C AK01B AK03A AK03B AK03D AK41B AK46B BA04 BA07 BA10A BA10D BA13 CB01 DA02 EH66C EJ38B GB16 HB31C JD02 JD03 JD04 JJ03 J01 BA04 J01 BAK BA43 BA44 CA07 CA12 DA02 FA01 GA14 LA24

Claims (9)

[Claims] 1. A packaging material for a tube container, wherein a surface polyolefin resin layer, a resin film having an inorganic oxide vapor-deposited film, and a back polyolefin resin layer are sequentially laminated. 2. The packaging material for a tube container according to claim 1, wherein the surface polyolefin-based resin layer has a printed pattern layer on one side thereof. 3. The packaging material for a tube container according to claim 1, wherein the resin film having an inorganic oxide vapor-deposited film has a printed pattern layer on one surface thereof. 4. The tube according to claim 1, wherein the inorganic oxide vapor-deposited film comprises a chemical vapor-deposited or physical vapor-deposited inorganic oxide vapor-deposited film. Packaging material for container. 5. The packaging material for a tube container according to claim 1, wherein the inorganic oxide vapor-deposited film comprises a silicon oxide vapor-deposited film formed by a chemical vapor deposition method. 6. The packaging material for a tube container according to claim 1, wherein the deposited film of the inorganic oxide comprises a deposited film of aluminum oxide formed by a physical vapor deposition method. 7. The method according to claim 1, wherein the resin film comprises a biaxially stretched polyester resin film, a biaxially stretched polyamide resin film, or a biaxially stretched polyolefin resin film. The packaging material for a tube container to be described. 8. A resin film provided with a front polyolefin resin layer and an inorganic oxide vapor-deposited film, or a resin film provided with an inorganic oxide vapor-deposited film and a back polyolefin resin layer are laminated. 8. The method according to claim 1, wherein the laminate is dry-laminated through an adhesive layer for use.
4. A packaging material for a tube container as described in 1. above. 9. A tube container packaging material having a structure in which a front polyolefin resin layer, a resin film having an inorganic oxide vapor-deposited film, and a back polyolefin resin layer are sequentially laminated. The surface of the surface polyolefin resin layer, which is the outermost layer at both ends of the tube container packaging material, and the surface of the back polyolefin resin layer, which is the innermost layer, are overlapped, and the opposing surfaces are heat-sealed. A tube container comprising a cylindrical body, and a head including a shoulder and a mouth provided at one opening of the cylindrical body.