JP2002179078A - Bag with pouring port - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a bag with a pouring port excellent in heat, pressure and water resistances, heat-sealing properties, resistance to thrust, resistance to pinhole formation, and lightproofness, further excellent in barrier properties for an oxygen gas, water vaport, etc., also capable of withstanding heat treatment and the like such as boiling treatment, further capable of reducing the quantity of refuse of containers and packaging materials and lowering the manufacturing cost of the bag, and excellent in packageability, shelf stability and the like for contents to be packed in the bag. SOLUTION: The bag is composed of a pouring port main body B consisting of a cylindrical mouth 1 and a boat-shaped bonded base portion 2 connected to the underside of the cylindrical mouth and a bag-like container main body fixed to the boat-shaped bonded base portion forming the pouring port main body. Further, the bag-like container main body is made of at least a laminated material in which a barrier layer provided with an inorganic oxide vapor- deposited film and a primer layer is laminated on one of faces of a base film and in which a lightproof layer provided with a metallized film and a heat- sealable resin layer are laminated on the other face of the base film in the order named.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bag with a spout, and more particularly, to heat resistance, pressure resistance, water resistance, heat sealability, pinhole resistance, piercing resistance, light shielding, Excellent in various physical properties such as others, furthermore, excellent in barrier properties to prevent permeation of oxygen gas, water vapor, etc., and also resistant to heat treatment etc. accompanying processing such as boiling treatment, and reduction of container and packaging waste. To reduce the production cost by shortening the production process, for example, juices, fruit juices, jelly-like beverages, nutritional drinks, drinking water, tea, coffee beverages, and milk. TECHNICAL FIELD The present invention relates to a packaging container useful for filling and packaging foods and beverages such as seasonings, oils, and others, and relates to a bag with a spout, which is excellent in the suitability of the contents for packing and preservation, storage suitability, and the like.

[0002]

2. Description of the Related Art Conventionally, plastic flexible packaging bags of various forms such as self-supporting bags, casset-type bags, and the like have been developed. Examples of such bags include juices, jelly-like beverages, nutritional drinks, and beverages. Water, tea, coffee drinks, milk, seasonings,
Packaging products in which various foods and drinks such as oils and the like are filled and packaged are sold. In particular, in recent years, the above-described self-supporting bags, gusset-type bags, and plastic soft packaging bags of various forms such as others, facilitate opening of the bags, and facilitate the beverage of the contents, or In order to make it easy to pour an object and to take it out easily, a packaged product or the like having a spout attached to an opening on one side of the bag has been proposed. These packaging products are easy to handle,
In addition, it has reclosability, etc.
That demand is growing.

Incidentally, in the bag-shaped container body constituting the plastic soft packaging bag to which the above-mentioned spout is attached, usually, in order to satisfy physical properties such as pinhole resistance,
Use a polyamide (nylon) resin film or sheet, and use a polyester resin film or sheet to satisfy physical properties such as heat resistance for attaching the spout. For example, in order to satisfy physical properties such as a barrier property for preventing permeation of oxygen gas, water vapor, etc., for example, polyvinylidene chloride resin, MXD nylon 6 resin, polyvinyl alcohol resin, Use of a film or sheet of a resin having a barrier property such as an ethylene-vinyl alcohol copolymer or the like, or a metal foil such as an aluminum foil. Use metal foil such as aluminum foil to satisfy physical properties,
Then, in order to make a bag with a heat seal or the like, a film or sheet of a polyolefin resin or the like is used. Thus, in order to manufacture a bag-shaped container body constituting a plastic soft packaging bag to which the above-mentioned spout is attached, the above-described packaging material is used, and a polyester resin film or sheet is usually used. Dry laminating through a laminating adhesive layer in a four-layer specification comprising a film or sheet of a polyamide (nylon) resin, an aluminum foil, and a film or sheet of a polyolefin resin or the like. Using a laminated method, a laminated material is manufactured by sequentially laminating them, and then using the laminated material,
The film or sheet of the innermost layer, such as a polyolefin resin, is heat-sealed with its surfaces facing each other to produce a bag, thereby producing bag-shaped container bodies of various forms. When using aluminum foil or the like,
Usually, a bag-shaped container body having both physical properties such as barrier properties and light-shielding properties can be manufactured.

[0004]

However, when a polyvinylidene chloride resin is used as the barrier material in the bag-shaped container body having the above-described structure, the permeation of oxygen gas, water vapor and the like is prevented. In the gas barrier property to have the expected effect, when used as a packaging container and then disposed of as garbage,
For example, when disposed of by incineration, etc., because it contains chlorine atoms, at the time of incineration disposal, for example, it may cause toxic gases such as dioxin, etc. There is a problem that it lacks suitability for disposal and causes problems such as environmental destruction, and also lacks environmental suitability. Also, as a barrier material, MX
In the case of using D nylon 6 resin, there is a problem in the moldability of forming the film or sheet, and the reality is that it is far from practical use. Further, when the above-mentioned polyvinyl alcohol-based resin or ethylene-vinyl alcohol copolymer is used as the barrier material, a gas barrier for preventing permeation of oxygen gas, water vapor and the like in a completely dry state. In the property, although it has the expected effect, in the wet state, the gas barrier property of preventing the permeation of oxygen gas, water vapor, etc. is significantly reduced,
There is a problem that it cannot be used.
Furthermore, when a metal foil such as an aluminum foil is used as a barrier material, it is extremely useful because it has excellent barrier properties and has a light-shielding property, but a metal foil such as an aluminum foil is There is a problem that pinholes are apt to be generated due to lack of bending resistance and the like, and the barrier property thereof is significantly impaired. Further, when used as a packaging container and then discarded as garbage, for example, incineration Metals such as aluminum remain when disposed of by disposal, etc., which may damage the incinerator, causing problems such as lack of suitability for disposal and environmental destruction, as well as lack of environmental suitability. Furthermore, metal foils such as aluminum foils have a problem that they are heavy and lack in reduction of container and packaging waste. Further, in the laminated material used for manufacturing the bag-shaped container body having the above-mentioned configuration, the dry laminating method or the like is performed with a four-layer specification through a laminating adhesive layer as described above. Since they are used to sequentially laminate them to produce a laminated material, there are problems that the production steps are many, complicated, and the production cost is increased. Therefore, the present invention is excellent in various physical properties such as heat resistance, pressure resistance, water resistance, heat sealability, pinhole resistance, puncture resistance, light shielding property, etc. Excellent barrier properties to prevent permeation, and also withstands heat treatment accompanying processing such as boiling.
In addition, containers and packaging waste are reduced, and the manufacturing process is shortened to reduce the manufacturing cost. For example, juices, fruit juices, jelly-like beverages, nutritional drinks, drinking water, Tea, coffee drink, milk, seasoning, oil,
It is an object of the present invention to provide a bag with a spout, which is a packaging container useful for filling and packaging other foods and drinks, and which is excellent in the suitability of the contents for packing and preservation, storage suitability and the like.

[0005]

The inventor of the present invention has conducted various studies to solve the above problems, and as a result, first, a cylindrical mouth and a boat-shaped adhesive base connected below the cylindrical mouth are connected. And a barrier layer provided with an inorganic oxide deposited film and a primer agent layer on one surface of the base film, and a metal layer on one surface of the base film. Using a laminated material obtained by sequentially laminating a barrier / light-shielding layer provided with a vapor-deposited film, and a heat-sealing resin layer, a self-supporting bag or a plastic soft packaging bag such as a casset-type bag. The bag-shaped container body constituting the bag is formed, and then the boat-shaped adhesive base constituting the spout body is brought into contact with the opening on one side of the bag-shaped container body, and both of them are At the abutting portion, it is fixed with a heat seal or the like, and A bag with a spout made of a container body is manufactured, and thereafter, the contents are filled in the bag with a spout.Furthermore, in the cylindrical mouth of the spout body constituting the bag with the spout described above. When a packaged product is manufactured by screwing a cap or the like that seals the opening through a screw portion or the like, heat resistance,
Excellent physical properties such as pressure resistance, water resistance, heat sealability, pinhole resistance, piercing resistance, light shielding properties, etc.
Excellent barrier properties to prevent transmission of oxygen gas, water vapor, etc.
Furthermore, it withstands the heat treatment accompanying the processing such as the boil processing, etc., and aims to reduce the amount of container and packaging waste and to shorten the manufacturing process to reduce the manufacturing cost.
For example, juices, fruit juices, jelly-like drinks, nutritional drinks, drinking water, tea, coffee drinks, milk, seasonings,
The present invention was found to be a packaging container useful for filling and packaging foods and beverages such as oils and the like, and to be able to manufacture a bag with a spout which is excellent in the filling and packaging suitability of its contents, storage suitability and the like. It is completed.

That is, according to the present invention, a spout main body comprising a cylindrical mouth and a boat-shaped adhesive base connected below the cylindrical mouth is fixed to a boat-shaped adhesive base constituting the spout main body. A bag-like container body, and further, the above-mentioned bag-like container body, at least, a barrier layer provided with an inorganic oxide vapor-deposited film and a primer agent layer on one surface of a substrate film, a substrate film A light-shielding layer provided with a metal deposition film on one side of,
Further, the present invention relates to a bag with a spout, characterized in that the bag is made from a laminated material in which a heat-sealing resin layer is sequentially laminated.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The above-described bag with a spout according to the present invention will be described in more detail below with reference to the drawings. FIG. 1 is a schematic perspective view showing an example of a spout main body constituting a bag with a spout according to the present invention,
FIG. 2 is a schematic perspective view showing an example of a bag-shaped container main body constituting a bag with a spout according to the present invention, and FIG. 3 is a schematic view showing an example of a bag with a spout according to the present invention. FIGS. 4 and 5 are schematic perspective views showing one example of a cap attached to a cylindrical mouth of a spout body constituting a bag with a spout according to the present invention. And FIG. 7 is a schematic perspective view showing an example of a spout body having another form with respect to the spout body constituting the bag with a spout according to the present invention, and FIG.
BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing which shows an example about the laminated material which forms the bag-shaped container main body which comprises the bag for retorts with an outlet according to this invention.

First, in the present invention, as shown in FIG. 3, a bag A with a spout according to the present invention comprises a tubular mouth and a boat-shaped adhesive base connected below the tubular mouth. The basic configuration is composed of an outlet main body B (FIG. 1) and a bag-shaped container main body C (FIG. 2) fixed to a boat-shaped adhesive base constituting the spout main body.

The spout main body B constituting the bag A with the spout according to the present invention will be described. As shown in FIG. The basic structure is that it comprises a boat-shaped adhesive base 2 connected below the cylindrical mouth 1. Further, the configuration of the spout body B will be described in detail. The cylindrical mouth portion 1 is provided with a thread 3 which is screwed to a cap described later.
Between the cylindrical mouth 1 and the boat-shaped adhesive base 2, an intermediate ring portion 4, and further, when the spout body B and the bag-shaped container body C are fixed, the spout body B is It has a structure provided with a large-diameter tubular portion 5 or a flange portion 6 necessary for gripping the spout body B when transporting or fixing both of them.

Next, with the spout according to the present invention described above.
The bag-shaped container body C constituting the bag A will be described.
Examples of the bag-shaped container body C include various shapes.
Plastic flexible packaging bags can be used.
To illustrate the example, as shown in FIG.
A plate 11 and a rear plate 12 are prepared.
Left and right side plates 13 and 14 with V-shaped P folded in on the sides
Then, the front plate 11, the rear plate 12, the left side plate 13 and the right side
Left and right ends, lower end (diagonal of both ends) where plate 14 overlaps
And bottom, etc.), and the left and right ends at the top.
Forming seal portions 15, 15,...
A gusset-shaped bag C having an opening 16 formed at its upper end. ₁ To
Can be used. Not shown in the present invention
However, of course, in the above gusset-type bag, one sheet
Right and left sides with a V-shape folded into the front plate, rear plate and inside from
And the end of the front or rear plate and the side plate.
Overlapping part, lower end part (diagonal part and bottom part at both ends) and above
Seal the left and right ends, etc., at the end and seal each.
Can be formed to form a gusset-shaped bag.
You. Further, in the present invention, the above-mentioned bag-shaped container main body is constituted.
The form of the bag to be formed can take various forms
In addition to the gusset-type bags as described above,
No, but for example, self-supporting bags, three-sided seal bags, four-sided seals
It is possible to use other types of bags, etc.
is there.

In the present invention, as shown in FIGS. 1 to 3, the spout-equipped bag A according to the present invention comprising the spout body B shown in FIGS. First, a spout body B including a tubular mouth 1 shown in FIG. 1 and a boat-shaped adhesive base 2 connected below the tubular mouth 1 is manufactured. On the other hand, a self-supporting bag or a gusset-type bag is used. A bag-shaped container body C made of a plastic soft packaging bag or the like is manufactured.
Then, a boat-shaped adhesive base 2 constituting the above-described spout body B is brought into contact with the spout body, and both of them are fixedly adhered to each other by a heat seal or the like at the contact portion, and the above-mentioned spout body is A bag A with a spout composed of B and the bag-shaped container body C described above is manufactured, and thereafter, contents and the like (not shown) are inserted into the bag A with a spout from the opening of the spout body B. Then, a cap D (shown in FIG. 4 described later) or the like is screwed through a thread 3 or the like provided in the cylindrical mouth portion 1 of the spout body B constituting the bag A with the spout. By sealing, a packaged product comprising the bag A with the spout according to the present invention can be manufactured.

As an example of the above-mentioned cap D, as shown in FIG. 4, as shown in FIG. the provided a peripheral side wall 23 grooves 22 may further include a cap D ₁ consisting of a ring portion 24 for connecting the lower end of the peripheral side wall 23. Further, in the present invention, another example of the above-mentioned cap D is illustrated as shown in FIG.
A peripheral wall 23 provided with a groove 22 so that it can be easily gripped on the peripheral surface thereof; in part, Pirufa via a plurality of connecting portions 25, 25 ... - pull - can be exemplified cap D ₂ having a circular body 26 having a full function.

In the above, the cap is
As a mechanism for exerting the pilfer-proof function,
It is possible to apply a known one, and it is not shown, for example, at the lower end of the screw 3 of the cylindrical mouth 1 of the above-described spout body B, and on the upper part of the intermediate ring 4 the jaw portion is provided in a continuous form or discontinuous shape, the other, above the cap D ₂ Pirufa - pull - in the inner surface of the annular body 26 having a full sexual function, continuous shape or not mating with said jaws continuous shape provided with a projection portion, and then, the cylindrical opening 1 of the infusion outlet body B, and screwing the cap D ₂ shown in FIG. 5 above, in the final stage of the screwing, the cap D ₂ Pirufa - The protrusion provided on the inner surface of the annular body 26 having a proof function is fitted to the jaw provided on the above-described spout body B, and
By the user, when it is opened the cap D ₂ initially is rotated along the cap D ₂ in screw thread 3, the cap D _2, the connecting portion 25 is broken, Pirufa - pull - off resistance The annular body 26 having a function separates,
And Thus, even if the cap removed D ₂ from the spout body B, Pirufa - pull - pull - - full sexual function is exhibited Pirufa by annular body 26 having a full sexual function is remaining on the spout body B Things. In the present invention, for example, if the cap is opened by mischief or the like at a retail store or the like, the state can be easily visually recognized, and the opening before use due to intentional or mere mischief is confirmed. It has the advantage that it can be done.

In the present invention, although not shown, the above-mentioned cap is fitted and locked with a packing material on an inner top surface constituting the cap by a fitting projection or the like provided on an inner side wall thereof. A cap having the configuration provided in the above manner can also be used. Thus, in the present invention, when the cap is provided with the above-described packing material, the cap is attached to the cylindrical mouth of the spout main body constituting the bag with the spout according to the present invention, and the cap is sealed. In addition, in the bag with a spout according to the present invention, the contents can be taken out and used, and further, the opening of the above-mentioned cylindrical mouth portion can be reused. When resealing is carried out, the resealing property can be extremely well enabled.

Although not shown in the present invention,
As described above, the inside of the bag with the spout according to the present invention is filled with contents and the like from the opening of the spout body, and then the opening of the cylindrical mouth of the spout body constituting the bag with the spout. To
A cover material or the like that seals the opening is sealed and fixed, and tightly adhered to produce a package. Thereafter, the package is boiled. A cap or the like is screwed through a thread or the like provided at the cylindrical mouth portion of the spout main body constituting the spouted bag, and the package is formed from the spouted bag according to the present invention by sealing. It can also be. Thus, the bag with a spout according to the present invention is:
As described above, heat resistance, pressure resistance, water resistance, barrier properties, heat resistance
It has excellent sealability and pinhole resistance, withstands the heat treatment associated with boil processing, etc., does not show any breakage of the bag or leakage of the contents, and functions as a food container, for example, filling the contents. It is capable of producing a packaged product excellent in packaging suitability, storage suitability, and the like.

Next, in the present invention, a note relating to the present invention
Another form of spout body B constituting bag A with outlet
An example of such a spout body B₁As
Is, as shown in FIG.₁Make up the boat shape
The four connecting portions 31, 31, 3 are formed below the adhesive base 2.
1, 31, and further between the connecting portions 31, 31, 31, 31
Are provided with four apertures 32, 32, 32, 32,
And the lower part of the above-mentioned four connecting parts 31, 31, 31, 31
To prevent blockage of the bag-shaped container body C, for example,
Whether the blockage prevention member 33 having a shape such as a mold is connected
Outlet body B ₁Can be used. Furthermore,
In the present invention, a bag A with a spout according to the present invention is configured.
An example of a further different form for the spout body B
If shown, such a spout body B_TwoAs shown in FIG.
Sea urchin outlet B_TwoUnder the boat-shaped adhesive base 2 that constitutes
On the other hand, the two connecting portions 31 and 31 and the connecting portion 3
Two apertures 32, 32 are provided between 1 and 31, so that
From the lower part of the two connecting parts 31, 31, a bag-shaped container
The shape of the body C is, for example, a cross shape to prevent the body C from being blocked.
Outlet body having a configuration in which blocking prevention members 33 are connected to each other.
B_TwoCan be mentioned. Thus, in the present invention,
As described above, for example, blockage prevention having a cross shape or the like
By providing the stop member, for example, the note according to the present invention is provided.
Fill the contents from the spout body that constitutes the bag with outlet
When closing the bag that constitutes the bag with the spout
To form a bag with a spout according to the present invention.
With a spout when sucking contents from the spout body
Prevents the bag that constitutes the bag from being closed, and satisfactorily
Can be taken out.

Next, in the present invention, the material, material, manufacturing method and the like constituting the bag with the spout according to the present invention will be described. First, the spout main body and cap forming the bag with the spout according to the present invention. Specific examples thereof include, for example, polyethylene resin, polypropylene resin, polystyrene resin, polycarbonate resin, polyester resin, polyamide resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile -It can be manufactured by using an injection molding method or the like using a resin having a high heat resistance such as a styrene-butadiene copolymer (ABS resin), a polyacetal resin, or the like. In the above,
In the same manner as described above, a cap or the like provided with an annular body having a pilfer-pulling function is also formed by injection molding using a resin such as described above and using a molding die or the like conforming to the shape. And the like. In the above description, the cap may be any one of a transparent body and an opaque body.

Next, in the present invention, the bag-shaped container body C constituting the bag with the spout according to the present invention will be described. The bag-shaped container body C is made of plastic soft packaging bags of various forms. What can be used. Thus, in the present invention, as shown in FIG.
A barrier layer 44 provided with an inorganic oxide vapor-deposited film 42 and a primer agent layer 43 on one side,
The laminated material E is formed by sequentially laminating a barrier / light-shielding layer 46 provided with a metal deposition film 45 on one surface of a, and a heat-sealing resin layer 47. Material E
The surfaces of the sealable resin layer 47 are superimposed on each other, and a seal portion is provided at a peripheral end thereof, so that a bag-shaped container body C having various forms can be formed. In the present invention, although not shown in the above laminated material E,
A surface of the primer agent layer 43 constituting the barrier layer 44;
A laminated material can also be manufactured by laminating the metal deposition film 45 constituting the barrier / light-shielding layer 46 so as to face the surface thereof, and if necessary, for the purpose of reinforcement, other, etc. A plastic material and the like can be arbitrarily selected and laminated to produce laminated materials having various forms.

In the above-mentioned laminated material, when, for example, a polyester resin film is used as the base film constituting the barrier layer, heat resistance,
It is possible to manufacture a bag-shaped container body having excellent physical properties such as bending resistance, and when a polyamide resin (nylon) film is used as a base film constituting a barrier and light shielding layer, for example. Is particularly capable of producing a bag-shaped container body having excellent pinhole resistance and the like. Further, in the above laminated material, the transmission of oxygen gas, water vapor, and the like is performed by two layers of the deposited film of the inorganic oxide forming the barrier layer and the deposited film of the metal forming the barrier and light shielding layer. Demonstrate effects such as barrier properties to prevent
Further, the above-mentioned metal vapor-deposited film exerts a function and effect such as light-shielding property, and ultimately, both of them, synergistically, exerts a function and effect such as barrier property and light-shielding property, such as aluminum foil. It exerts the same effects as the metal foil, such as barrier properties and light-shielding properties. Further, in the above laminated material, the deposited film of the inorganic oxide constituting the barrier layer, and the deposited film of the metal constituting the barrier and light-shielding layer, and the like,
As will be described later, the film thickness is several tens to several thousand degrees, for example, compared with a metal foil such as an aluminum foil having a film thickness of about 5 to 20 μm, the film thickness is The thickness and the weight can be significantly reduced, whereby the weight can be significantly reduced and the amount of container / packaging waste can be reduced. Furthermore, in the above-mentioned laminated material, as described later, an organic silicon compound is used as a monomer gas for vapor deposition, and a vapor-deposited silicon oxide film formed by plasma chemical vapor deposition is used as a barrier. When used as a deposited film of an inorganic oxide constituting the conductive layer, the deposited film of silicon oxide is rich in flexibility and has flexibility and the like. This has the advantage of not lowering the performance.

Next, in the present invention, the materials constituting the above-mentioned laminated material, the manufacturing method thereof, and the like will be described.
The same base film constituting the barrier layer or the same base film constituting the barrier / light-shielding layer can be used. Thus, in the present invention,
As the above substrate film, these are bag-shaped container body C
Because it is a basic or auxiliary material that constitutes the material, and furthermore, it is a base material that holds a vapor-deposited film of an inorganic oxide or a metal, and so on, first, heating during bag making, workability, etc. It has excellent physical properties such as heat resistance, slipperiness, pinhole resistance, etc., and can hold them well without impairing the properties of inorganic oxide deposited films, metal deposited films, etc. A resin film or sheet that satisfies the requirements such as what can be achieved and others can be used. In the present invention, examples of the resin film or sheet include, for example, polyolefin resins such as polyethylene resins or polypropylene resins, cyclic polyolefin resins, polystyrene resins, and acrylonitrile-styrene copolymers. Coalesced (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), poly (meth) acrylic resin, polycarbonate resin, polyethylene terephthalate,
Uses films or sheets of various resins such as polyester resins such as polyethylene naphthalate, polyamide resins such as various nylons, polyurethane resins, acetal resins, cellulose resins, etc. can do. In the present invention, among the resin films or sheets described above, 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 the extrusion method, the cast molding method, the T-die method, and the cutting method are used. 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 various resins. A film or 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,
For the purpose of improving or modifying the antioxidant properties, slip properties, mold release properties, flame retardancy, anti-mold properties, electrical properties, strength, etc., various plastic additives and additives can be added. 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 be optionally used to improve the tight adhesion with an inorganic oxide deposited film or a metal deposited film. A desired surface treatment layer can be provided in advance. In the present invention, as the surface treatment layer, for example, a corona discharge treatment, an ozone treatment, a low-temperature plasma treatment using an oxygen gas or a nitrogen gas, a glow discharge treatment, an oxidation treatment using a chemical or the like, Any other pretreatment such as, for example, 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 surface pretreatment,
This method is carried out as a method for improving the tight adhesion between a film or sheet of various resins and a deposited film of an inorganic oxide or a deposited film of a metal. In addition, for example, a primer coat agent layer, an undercoat agent layer, an anchor coat agent layer, an adhesive layer, A surface treatment layer may be formed by arbitrarily forming a vapor-deposited anchor coating agent layer or the like. As the coating agent layer of the above pretreatment, for example, polyester-based resin,
Polyolefin resins such as polyamide resins, polyurethane resins, epoxy resins, phenol resins, (meth) acrylic resins, polyvinyl acetate resins, polyethylene aliha polypropylene, or copolymers or modified resins thereof, cellulose And a resin composition containing, as a main component of the vehicle, a base resin or the like.

Next, in the present invention, the deposited film of the inorganic oxide constituting the barrier layer will be described. First, as the deposited film of the inorganic oxide, for example, a vacuum deposition method, a sputtering method, an ion plating method, or the like. Physical vapor deposition methods such as the pitting method and the ion cluster beam method
cal Vapor Deposition method, PVD
Method). In the present invention,
Specifically, a metal oxide is used as a raw material, and this is heated to be vapor-deposited on a base film, or a metal or metal oxide is used as a raw material, and oxygen is introduced and oxidized. Then, an amorphous thin film of an inorganic oxide can be formed by using an oxidation reaction vapor deposition method of depositing the film on a base film and further using a plasma assisted oxidation reaction vapor deposition method of promoting the oxidation reaction 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 inorganic oxide deposited film, basically, any thin film obtained by depositing a metal oxide can be used. For example, silicon (Si),
Aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (P
b), a deposited film of an oxide of a metal such as zirconium (Zr) or yttrium (Y) can be used. Thus, a preferable example is a deposited film of an oxide of a metal such as silicon (Si) and aluminum (Al). And Thus, deposited films of oxides of the above metals, silicon oxides, aluminum oxides, can be referred to as a metal oxide like such as magnesium oxide, the notation is, for example, SiO _X, AlO _X , MO _X (in the formula, M represents a metal element, the value of X is in the range respectively by the metal element is different.) as such MgO _X represented by. The range of the value of X is silicon (S
i) is 0-2, and aluminum (Al) is 0-1.
5. Magnesium (Mg) is 0-1, calcium (C
a) is 0-1, potassium (K) is 0-0.5, tin (Sn) is 0-2, and sodium (Na) is 0-0.
5, boron (B) is 0 to 1,5, titanium (Ti) is
0-2, lead (Pb): 0-1, zirconium (Zr)
Can take a value in the range of 0 to 2 and yttrium (Y) can take a value in the range of 0 to 1.5. In the above, when X = 0,
It is a perfect metal, is not transparent and cannot be used at all, and the upper end of the range of X is a fully oxidized value. In the present invention, generally, except for silicon (Si) and aluminum (Al), examples used are scarce. Silicon (Si) is 1.0 to 2.0, aluminum (A)
For l), a value in the range of 0.5 to 1.5 can be used. In the present invention, the thickness of the above-described inorganic oxide vapor-deposited film varies depending on the type of metal or metal oxide to be used.
It is desirable to arbitrarily select and form in the range of about 000 °, preferably about 100 to 1000 °. Also, in the present invention, the metal to be used as the inorganic oxide vapor-deposited film or the metal oxide is one or two kinds.
It is also possible to form a deposited film of an inorganic oxide mixed with different materials by using a mixture of more than one kind.

Next, in the present invention, a specific example of a method for forming the above-mentioned vapor-deposited film of an inorganic oxide will be described. FIG. . As shown in FIG. 9, an unwinding roll is placed in a vacuum chamber 52 of a take-up type vacuum evaporation apparatus 51.
The base film 54 unwound from the roll 53 is cooled by a cooled coating drum 57 via guide rolls 55 and 56.
Will be guided to. Thus, on the base film 54 guided on the cooled coating drum 57, the evaporation source 59 heated by the crucible 58, for example, metal aluminum or aluminum oxide is evaporated. Further, if necessary, an oxygen gas or the like is ejected from the oxygen gas outlet 60, and a vapor-deposited film of, for example, an inorganic oxide such as aluminum oxide is formed through the masks 61 while supplying the gas. Things. Then, in the present invention,
In the above, for example, the base film 54 on which a vapor-deposited film of an inorganic oxide such as aluminum oxide is formed is taken up on a take-up roll 64 or the like via guide rolls 62, 63, etc. A substrate film having a vapor-deposited oxide film can be manufactured. 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 above-mentioned inorganic oxide deposited film can be formed by, for example, a chemical vapor deposition method or the like. Chemical vapor deposition methods such as chemical vapor deposition and photochemical vapor deposition
It can be formed by a method such as a position method or a CVD method. More specifically, on one side of the base film,
Low-temperature plasma generation using a monomer gas for vapor deposition of an organic silicon compound or the like as a raw material, an inert gas such as an argon gas or a helium gas as a carrier gas, and an oxygen gas or the like as an oxygen supply gas. A deposited film of an inorganic oxide such as silicon oxide can be formed by a low-temperature plasma chemical vapor deposition method using an apparatus or the like. In the above,
As the low-temperature plasma generator, for example, a high-frequency plasma, a pulsed-wave plasma, a generator such as a microwave plasma can be used, and in the present invention,
In order to obtain highly active and stable plasma, it is desirable to use a generator based on 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 low-temperature plasma chemical vapor deposition method will be described. FIG. FIG. 1 is a schematic configuration diagram of a low-temperature plasma chemical vapor deposition apparatus showing an outline of a method of forming an oxide deposition film. As shown in FIG. 10 described above, in the present invention, a base film 74 is unwound from an unwinding roll 73 disposed in a vacuum chamber 72 of a plasma enhanced chemical vapor deposition apparatus 71. Film 74
The cooling roller is conveyed onto the peripheral surface of the electrode drum at a predetermined speed via an auxiliary roll. Thus, in the present invention, oxygen gas, an inert gas, a monomer gas for vapor deposition of an organic silicon compound, etc., and the like are supplied from the gas supply devices 77 and 78 and the raw material volatilization supply device 79 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 72 through the raw material supply nozzle 80, and was transferred onto the peripheral surface of the cooling / electrode drum 76 described above. Plasma is generated by the glow discharge plasma 81 on the base film 74 and is irradiated with the plasma 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 electric power is applied to the cooling / electrode drum 76 from the power source 82 disposed outside the chamber.
In the vicinity of 6, a magnet 83 is arranged to promote the generation of plasma. Then, the base film 74 on which the deposited film of an inorganic oxide such as silicon oxide is formed is guided to a guide roll 84 or the like. The substrate film having the inorganic oxide vapor-deposited film according to the present invention can be manufactured by winding the film on a winding roll 85 or the like. In the figure, 86 is
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, the deposited film of the inorganic oxide is not limited to one layer of the deposited film of the inorganic oxide, and may be a multilayer film in which two or more layers are laminated. Alternatively, a vapor-deposited film of an inorganic oxide which is used as a mixture of two or more kinds and is mixed with different materials can also be formed.

In the above, the inside of the vacuum chamber 72 is
The pressure is reduced by the empty pump 86 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. In addition, in the raw material volatile supply device 79,
And the gas supply devices 77 and 78
Mixed with oxygen gas, inert gas, etc. supplied from
Vacuum gas through the raw material supply nozzle 80
−72. 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 76
Since the voltage is applied, the source in the vacuum chamber 72 is
Between the opening of the material supply nozzle 80 and the cooling / electrode drum 76
Glow discharge plasma 81 is generated in the vicinity, and this glow discharge plasma 81 is generated.
The discharge plasma 81 is composed of one or more gas components in a mixed gas.
Minutes, and in this state, the substrate
The film 74 is transported at a constant speed, and a glow discharge plug is used.
The substrate 81 on the peripheral surface of the cooling / electrode drum 76 is
On the film 74, a deposited film of an inorganic oxide such as silicon oxide is formed.
It can be formed. In addition, true at this time
The degree of vacuum in the empty chamber is 1 × 10^-1~ 1 × 10^-FourT
orr level, preferably 1 × 10 vacuum^-1~ 1 × 10^-2
It is desirable to adjust to the Torr position,
The transport speed of LUM 74 is preferably about 10 to 300 m / min.
In particular, it is desirable to adjust to 50 to 150 m / min.
Things.

The above-mentioned plasma chemical vapor deposition apparatus 7
In (1), a vapor-deposited film of an inorganic oxide such as silicon oxide is formed on the base film 74 in the form of SiO _{x in} the form of a thin film 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, S
The iO _X plasma surface of the base film 74 is cleaned, the surface of the base film 74, a polar group and pretend - since radicals such as occurs, a deposited film of an inorganic oxide such as silicon oxide is formed This has the advantage that the close adhesion with the base film 74 is high. Further, 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 Torr. ^-2 Torr, so that 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 × 10
^{Since the} degree of vacuum is lower than ^-5 Torr, the time for setting the vacuum state when exchanging the base film 74 can be shortened, the degree of vacuum is easily stabilized, and the film forming process is stabilized. Things.

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 a substrate 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, 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. In general, the gas permeability decreases as the value of X decreases, but the film itself does Is yellowish,
Transparency worsens.

The above-mentioned 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 comprising a deposited film containing the kind by chemical bonding 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 the form of graphite, diamond, fullerene, 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, the type, amount, and the like of the compound contained in the deposited silicon oxide film can be changed by changing the conditions and the like of the deposition process. Thus, the content of the above compound in the deposited silicon oxide 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 above, the impact resistance and the like can be enhanced by the above-mentioned compounds and the like, while at the interface with the base film, the content of the above-mentioned compounds is small, so that the base film and the deposited film of silicon oxide Has the advantage that the tight adhesion of the polymer becomes strong.

According to the present invention, the above-mentioned silicon oxide deposited film may be, 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, 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 properties and the like. In the above, for example, an argon gas, a helium gas, or the like can be used as the inert gas.

Next, in the present invention, the primer agent layer constituting the above-mentioned barrier layer will be described. As the primer agent layer, first, a polyurethane resin or a polyester resin is used as a main component of the vehicle, The silane coupling agent is about 0.05 to 10% by weight, preferably about 0.1 to 5% by weight, and the filler is 0.1 to 20% based on 1 to 30% by weight of the polyurethane resin or polyester resin. % By weight, preferably about 1 to 10% by weight, and further, if necessary, a stabilizer, a curing agent,
Additives such as a crosslinking agent, a lubricant, an ultraviolet absorber, and the like are optionally added, and a solvent, a diluent, and the like are added and mixed well to prepare a resin composition. Thus, the above-prepared resin composition was used and, for example, roll coat, gravure coat, knife coat, dip coat, spray coat,
By another coating method or the like, coating is performed on the inorganic oxide vapor-deposited film provided on one surface of the base film, and thereafter, the coating film is dried to form a solvent,
The diluent or the like is removed, and if necessary, aging treatment or the like is 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 to} 5.0 g / m ^2.
2 (dry state) is desirable. Thus, in the present invention, with the above-described primer agent layer, a vapor-deposited film of an inorganic oxide, a barrier / light-shielding layer or the like in which a metal vapor-deposited film is provided on one surface of a base film. And the elongation of the primer agent layer are improved, and for example, the post-processing suitability such as laminating or box forming is improved, and the inorganic oxide is deposited during the post-processing. This prevents the occurrence of cracks and the like in the film.

In the above, as the polyurethane resin constituting the above 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, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, etc.
Or polyfunctional isocyanates such as aliphatic polyisocyanates such as hexamethylene diisocyanate and xylylene diisocyanate; and polyether polyols.
One- or two-component curing type polyurethane resins obtained by reaction with a hydroxyl group-containing compound such as polyester, polyester polyol, polyacrylate polyol or the like can be used. Thus, in the present invention,
By using a polyurethane-based resin as described above, the adhesion between the vapor-deposited film of the inorganic oxide and the barrier / light-shielding layer and the like are improved, and the elongation of the primer agent layer is improved. For example, laminating or
The purpose of the present invention is to improve the suitability for post-processing such as box making and prevent the occurrence of cracks and the like in the deposited film of the inorganic oxide during the post-processing.

In the above, the polyester resin constituting the above resin composition includes, for example, one or more aromatic saturated dicarboxylic acids having a benzene nucleus as a basic skeleton such as terephthalic acid, and a saturated resin. A thermoplastic polyester resin formed by polycondensation with one or more divalent alcohols can be used. In the above, examples of the aromatic saturated dicarboxylic acid having a benzene nucleus as a basic skeleton include, for example, terephthalic acid, isophthalic acid, phthalic acid, and diphenyl ether-
4,4-dicarboxylic acid and others can be used. In the above, as the saturated divalent alcohol, ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, polypropylene glycol, Polytetramethylene glycol, hexamethylene glycol, dodecamethylene glycol,
Aliphatic glycols such as neopentyl glycol; alicyclic glycols such as cyclohexanedimethanol; 2.2.
Bis (4'-β-hydroxyethoxyphenyl) propane, naphthalenediol, other aromatic di-, and the like can be used.

In the present invention, as the polyester resin, specifically, for example, thermoplastic polyethylene terephthalate resin formed by polycondensation of terephthalic acid and ethylene glycol, terephthalic acid and tetramethylene Thermoplastic polybutylene terephthalate resin formed by polycondensation with glycol, terephthalic acid and 1,4
-Thermoplastic polycyclohexane dimethylene terephthalate formed by polycondensation with cyclohexane dimethanol
Resin, thermoplastic polyethylene terephthalate resin formed by copolycondensation of terephthalic acid, isophthalic acid and ethylene glycol, terephthalic acid and ethylene glycol
Thermoplastic terephthalate resin formed by the copolycondensation of toluene and 1,4-cyclohexanedimethanol, formed by the copolycondensation of terephthalic acid, isophthalic acid, ethylene glycol and propylene glycol Thermoplastic polyethylene terephthalate resin, polyester polyol resin and the like can be used. In the present invention, a saturated aromatic dicarboxylic acid having a benzene nucleus as a basic skeleton as described above further includes, for example,
Malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, can be copolycondensed by adding one or more aliphatic saturated dicarboxylic acids such as dodecanoic acid, It is preferable to use about 1 to 10% by weight of aromatic saturated dicarboxylic acid having a benzene nucleus as a basic skeleton. Thus, in the present invention, by using the polyester resin as described above, the adhesion between the vapor-deposited film of the inorganic oxide and the above-mentioned barrier / light-shielding layer and the like can be improved and the primer agent can be used. It is intended to improve the elongation of the layer, for example, to improve the post-processing suitability such as laminating or box-forming, and to prevent the occurrence of cracks or the like in the deposited film of the inorganic oxide during the post-processing. .

Next, in the above, as the silane coupling agent constituting the above resin composition, an organic functional silane monomer having dual reactivity can be used. For example, γ-chloropropyl Trimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris (β-methoxyethoxy) silane,
γ-methacryloxypropyltrimethoxysilane, β
-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, N-β (aminoethyl)-
γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane, γ- One or more of aqueous solutions of aminopropylsilicone and the like can be used.

The above-mentioned silane coupling agent hydrolyzes a functional group at one end of the molecule, usually, a chloro, alkoxy, or acetoxy group, and forms 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, a strong bond is formed by reacting with the material constituting the barrier / light-shielding layer, other layers, and the like described above. Further, through the above-mentioned barrier and light-shielding layer and the like, other substrates and the like are firmly and tightly adhered to each other, and the laminating strength is increased. Thus, in the present invention, This makes it possible to form a strong laminated structure having high laminate strength. In the present invention, utilizing the inorganic and organic properties of the silane coupling agent, other base materials and the like, through a layer such as a vapor-deposited film of an inorganic oxide and the above-mentioned barrier and light-shielding layer, etc. To improve the tight adhesion with the resin, thereby significantly increasing the laminating strength and the like.

Next, in the present invention, as a filler constituting the above resin composition, for example, calcium carbonate,
Barium sulfate, alumina white, silica, talc, glass frit, resin powder, and the like can be used. Thus, the above-mentioned filler adjusts the viscosity and the like of the above-mentioned resin composition liquid, improves its coating suitability, and combines a silane coupling agent with a polyurethane resin or polyester resin as a binder resin. To improve the cohesive force of the coating film.

In the present invention, in addition to the above-mentioned primer agent layer composed of a coating film made of the resin composition, furthermore, for example, a polyamide resin or an epoxy resin , Phenolic resin,
Use of (meth) acrylic resin, polyvinyl acetate resin, polyolefin resin such as polyethylene or polypropylene, or a copolymer or modified resin thereof, cellulose resin, etc. Thus, a primer agent layer can be formed. In the present invention, a primer coating agent layer is formed by coating using a coating method such as roll coating, gravure coating, kiss coating, or the like. Therefore, the coating amount is desirably about 0.1 to 10 g / m ² (dry state).
In the present invention, it is most effective to use, as the primer agent layer, a primer agent layer made of a resin composition containing the above-mentioned polyurethane resin or polyester resin as a main component of the vehicle. .

Next, in the present invention, the metal deposited film constituting the above-mentioned barrier / light-shielding layer will be described.
Examples of such a metal vapor-deposited film include physical vapor deposition methods such as the above-described vacuum vapor deposition method, sputtering method, ion plating method, and ion cluster beam method.
cal Vapor Deposition method, PVD
Method). In the present invention,
Specifically, using a roll-up type vacuum evaporation apparatus shown in FIG. 9 described above, using a metal such as aluminum as a raw material, heating the metal and depositing it on a base film using a vacuum evaporation method or the like. A metal deposition film can be formed. 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 metal deposition film, basically, any thin film obtained by vapor deposition of a metal can be used. For example, silicon (Si), aluminum (Al), magnesium ( Mg), calcium (C
a), potassium (K), tin (Sn), sodium (N
a), a vapor deposited film of a metal such as boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y), or the like can be used. Thus, a preferable example is a deposited film of a metal such as aluminum (Al). In the present invention, the thickness of the above-mentioned metal vapor-deposited film varies depending on the type of metal used and the like, but is, for example, arbitrarily selected within the range of about 50 to 4000 °, preferably about 100 to 1000 °. It is desirable to form it. In the present invention,
As a metal vapor deposition film, a mixture of two or more kinds of metals to be used may be used to form a metal vapor deposition film mixed with different materials.

Next, in the present invention, the heat-sealing resin layer constituting the above-mentioned laminated material may be any material that can be melted by heat and fused to each other. Medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-
Acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, methylpentene polymer, polyethylene, polyolefin resin such as polypropylene, acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, An acid-modified polyolefin resin modified with an unsaturated carboxylic acid such as another resin, a resin film or sheet composed of one or more kinds of other resins, or a coating film thereof can be used. The above-mentioned resin film or sheet can be used in a single layer or multilayer, and the above-mentioned resin film or sheet can be used.
The thickness of the gate is about 5 μm to 300 μm, preferably about 10 μm to 110 μm. Further, in the present invention, the thickness of the resin film or sheet described above may be determined when the bag-like container body is made or when a bag with a spout is manufactured. In order to prevent the occurrence of scratches, or cracks, etc. on the deposited film of the object or the deposited film of the metal constituting the barrier / light-shielding layer, it is preferable to increase the thickness relatively. Specifically, 70 μm to 110 μm
It is preferably about m, preferably about 80 μm to 100 μm.

In the present invention, among the above resin films or sheets, it is particularly preferable to use linear low-density polyethylene. That is, the above-mentioned linear low-density polyethylene has the advantage of improving the impact resistance with less propagation of breakage due to its tackiness, and also because the inner layer is constantly in contact with the contents. It is also effective for preventing the deterioration of the environmental stress cracking resistance.
In the present invention, the linear low-density polyethylene,
Other resins can also be blended, for example, by blending ethylene-butene copolymer or the like,
Although heat resistance is poor and seal stability tends to deteriorate in a high-temperature environment, there is an advantage that tearability is improved and contributes to easy opening.

Further, in the present invention, the above-mentioned
Specific examples of the linear low-density polyethylene as a resin film or sheet having sealability include a film or sheet of an ethylene-α-olefin copolymer polymerized using a metallocene catalyst. It can be used as well. Examples of the film or sheet of the ethylene-α-olefin copolymer polymerized using the metallocene catalyst include, for example, a catalyst obtained by combining a metallocene complex such as a catalyst obtained by combining zirconocene dichloride and methylalumoxane with alumoxane. That is, an ethylene-α-olefin copolymer film or sheet obtained by polymerization using a metallocene catalyst can be used. The metallocene catalyst is a so-called multi-site catalyst in which the active sites are non-uniform and the current catalyst is called a single-site catalyst because the active sites are uniform. Specifically, Mitsubishi Chemical Corporation's product name "Kernel", Mitsui Petrochemical Industry Co., Ltd. product name "Evolu", USA, Exxon Chemical (E
XXON CHEMICAL's product name “EXACT”, Dow Chemical, USA (DOW)
"Affinity- (A
FFINITY), trade name "ENGAG (ENGAG)
E) ethylene-polymerized using a metallocene catalyst such as
An α-olefin copolymer film can be used. The film or sheet can be used in a single layer or a multilayer, and the thickness is 5 μm
To about 300 μm, preferably 10 μm to 10 μm.
About 0 μm is desirable. In the present invention, when a film or sheet of an ethylene-α-olefin copolymer polymerized using a metallocene catalyst is used as the heat-sealing resin film as described above, a bag may be used. It has the advantage that low temperature heat sealability is possible when producing the body.

Usually, packaging bags are subjected to severe physical and chemical conditions, so that the laminated material constituting the packaging bags is required to have strict packaging suitability, and the deformation prevention strength is required. And various conditions such as drop impact strength, pinhole resistance, heat resistance, sealing, quality maintenance, workability, hygiene, etc., are required. In addition to the material, any other material that satisfies the above conditions can be used arbitrarily.
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 (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin, polycarbonate -Bonnet tree Films of known resins such as polyvinyl alcohol-based resin, saponified ethylene-vinyl acetate copolymer, fluorine-based resin, diene-based resin, polyacetal-based resin, polyurethane-based resin, nitrocellulose, etc. The sheet 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 may be any of unstretched and uniaxially or biaxially stretched. The thickness is arbitrary, but can be selected from a range of several μm to about 300 μm. Further, in the present invention, as the film or sheet, extrusion film formation,
Any film such as an inflation film or a coating film may be used.

In particular, in the present invention, other base materials include, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, Coloring such as polypropylene, ethylene-propylene copolymer and other resin-based films or sheets, coloring agents such as pigments, and other additives, and other additives are added and kneaded to form a film. Resin films or sheets can be used. These materials can be used alone or in combination of two or more. The thickness of the film or sheet is arbitrary, but is usually about 5 μm to 300 μm,
A thickness of about 10 μm to 100 μm is desirable.

Next, a method of manufacturing a laminated material using the above-described materials in the present invention will be described. Examples of the method include a laminating method used when manufacturing a normal packaging material. For example, wet lamination, dry lamination, solventless lamination, extrusion lamination, co-extrusion lamination, inflation, and other methods can be used. Thus, in the present invention, when performing the above-mentioned lamination, if necessary, for example, a pretreatment such as a corona treatment, an ozone treatment, and a framing treatment is optionally performed on the surface of the substrate to be laminated. be able to. In the above, when extrusion lamination is performed, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin A polyolefin resin such as ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, methylpentene polymer, polyethylene, polypropylene, etc. An acid-modified polyolefin resin modified with an unsaturated carboxylic acid such as methacrylic acid, maleic anhydride, fumaric acid, and the like can be used as a resin for extrusion. At that time, as an adhesion assistant, for example, an isocyanate-based, polyethyleneimine-based or other anchor coating agent or the like can be optionally used. In the present invention, when dry laminating, for example, a solvent type, an aqueous type, and an emulsion type containing vinyl, acrylic, polyurethane, polyamide, polyester, epoxy, or the like as a main component of a vehicle. , And other adhesives for laminating can be used. Thus, in the present invention, a barrier layer comprising the above-mentioned bag-shaped container main body, which is provided with at least one surface of the base film provided with an inorganic oxide deposition film and a primer agent layer, In order to manufacture a laminated material obtained by sequentially laminating a barrier / light-shielding layer provided with a metal vapor-deposited film on one surface of a material film, and a heat-sealing resin layer,
Using a tandem extrusion laminating machine and laminating in one step with a dry laminating method via a laminating adhesive layer to produce a laminated material can reduce the number of steps. This is a preferred production method.

Next, in the present invention, a bag-shaped container body manufactured by using the above-described laminated material will be described. The bag-shaped container body uses the above-described laminated material, Then, the peripheral resin is heat-sealed at its peripheral end to form a seal portion, thereby producing a bag-shaped container body having an opening at the upper end. Can be bag. Thus, as a bag making method, the above-described laminated material is folded or overlapped,
The surfaces of the inner layers are opposed to each other, and the peripheral end portions thereof are, for example, a side seal type, a two-side seal type, a three-side seal type, a four-side seal type, an envelope-attached seal type, and a gasket. Heat seals such as adhesive seal type (pyro-seale type), pleated seal type, flat bottom seal type, square bottom seal type, gusset type, etc. To produce bag-shaped container bodies of various forms having an opening at the upper end. In addition, as the bag-like container body, for example, a self-supporting packaging bag (standing pouch) or the like can be used. In the above, as a method of heat sealing, for example,
Roll, rotary roll seal, belt seal, impulse seal
It can be performed by a known method such as a seal, a high-frequency seal, an ultrasonic seal, or the like.

Next, in the present invention, as described above, the method of attaching the spout body to the opening of the bag-shaped container body having an opening at the upper end as described above is as follows. A boat-shaped adhesive base constituting the above-mentioned spout body is brought into contact with the opening at the upper end of the spout, and the two parts are, for example, a bar seal and a rotary roll seal at the contact portions. , Belt seal, impulse seal, high frequency seal
A bag with a spout comprising a spout body and a bag-like container body can be manufactured by tightly bonding with a heat seal or the like by a known method such as a seal or an ultrasonic seal. is there. Next, in the present invention, the spout-equipped bag according to the present invention is filled with the contents from the opening of the spout main body, and then the cylindrical spout of the spout main body constituting the spout-equipped bag is formed. By screwing a cap or the like through a thread or the like provided in the part and sealing the cap, a packaged product comprising a bag with a spout according to the present invention can be manufactured. Alternatively, in the present invention, in the bag with the spout according to the present invention, the contents are filled through the opening of the spout main body, and a sealing material for sealing the opening is fixed to the opening. Then, the package is manufactured, and thereafter, the package is boiled, and then, similarly to the above, a screw or the like provided at the cylindrical mouth portion of the spout body constituting the bag with the spout. By screwing a cap or the like through the airtight container and sealing it, a packaged product comprising the bag with a spout according to the present invention can also be manufactured. In the above, as a method of boiling, for example, a method of boiling at a temperature of about 90 to 100 ° C., preferably about 90 ° C., time, about 5 to 20 minutes, preferably about 10 minutes is performed. be able to. Thus, in the present invention, the contents can be subjected to heat sterilization, heat sterilization cooking, or the like by the above-described boil processing.

Next, in the present invention, the contents to be filled and packaged in the bag with a spout according to the present invention include, for example, liquid food such as porridge, jelly-like food, liquid soup, seasoning,
Examples include liquid foods such as curry, stew, meat sauce, and others. Thus, the bag with a spout according to the present invention is excellent in heat resistance, pressure resistance, water resistance, heat sealability, pinhole resistance, piercing resistance, transparency, etc.
Furthermore, it is excellent in barrier properties to prevent permeation of oxygen gas, water vapor, etc., and also withstands heat treatment accompanying processing such as retort treatment or boiling treatment. For example, juices, fruit juices, jelly drinks , Energy drinks, drinking water, tea,
It is a packaging container useful for filling and packaging foods and beverages such as coffee drinks, milk, seasonings, oils, and others, and has excellent filling and packaging suitability and preservation suitability for its contents.

[0054]

Next, the present invention will be described more specifically with reference to examples of the present invention. Example 1 (1). Using a polypropylene resin, the polypropylene resin is melted at about 200 ° C., and injection-molded using an injection molding method, and the cylindrical mouth has an inner diameter of 8.5 mm, an outer diameter of 8.5 mm.
A spout body consisting of 11 mm, height, 20 mm, and a boat-shaped adhesive base having a width, 20 mm, height, 10 mm was manufactured (see FIG. 1). (2). In the same manner as in (1) above, a cap was formed by injection molding using a polypropylene resin and capable of being screwed onto the cylindrical mouth of the spout body. In addition, on the inner top surface of the above cap, a thickness 1 made of polyethylene sheet was used.
mm packing material was fitted and locked (see FIG. 4). (3). On the other hand, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used, and was mounted on a delivery roll of a plasma enhanced chemical vapor deposition apparatus. Sauce
On the corona-treated surface of the film, a deposited film of silicon oxide having a thickness of 200 ° was formed. (Evaporation conditions) Evaporation surface; Corona treated surface Introduced gas amount: Hexamethyldisiloxane: Oxygen gas: Helium = 1.0: 3.0: 3.0 (unit: slm) Degree of vacuum in vacuum chamber; 6 × 10 ⁻⁶ mBar Degree of vacuum in the deposition chamber; 2 to 5 × 10 ⁻³ mBar Cooling / electrode drum supply power; 10 kW Line speed; 100 m / min Immediately after the formation, a glow-discharge plasma generator was used to apply a power of 9 kW, oxygen gas (O ₂ ): argon gas (Ar) = 7.0: 2.5 ( Unit: slm) is used, and the mixed gas pressure is 6
× 10 ⁻⁵ Torr, 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. Next, on the plasma-treated surface formed above, to the initial condensate of the polyurethane resin,
A polyurethane resin composition obtained by adding an epoxy silane coupling agent (8.0% by weight) and an antiblocking agent (1.0% by weight) and sufficiently kneading the mixture is used. 0.5 g / m ²
(Dry state), and then dried to form a primer layer, thereby forming a barrier layer. (4). Further, a biaxially stretched nylon 6 film having a thickness of 15 μm was used, which was mounted on a delivery roll of a take-up type vacuum evaporation apparatus, and then fed out onto a coating drum to perform corona treatment. On the surface, aluminum was used as a deposition source under the following conditions, and a film thickness of 200 was formed by a vacuum deposition method using an electron beam (EB) heating method.
An aluminum vapor-deposited film was formed. (Evaporation conditions) Evaporation source: Aluminum Degree of vacuum in vacuum chamber: 7.5 × 10 ⁻⁶ mbar Degree of vacuum in evaporation chamber: 2.1 × 10 ⁻⁶ mbar EB output: 20 KW Film transport speed: 600 m / Next, a 200-nm-thick aluminum vapor-deposited film was formed as described above to form a barrier / light-shielding layer. (5). Next, after forming a desired printed pattern on the surface of the primer agent layer of the barrier layer formed in the above (3), a two-part curable polyurethane laminate is applied over the entire surface including the printed pattern. The adhesive for coating is coated to a thickness of 4.0 g / m ² (dry state) by a gravure roll coating method to form an adhesive layer for laminating, and then the adhesive for laminating is applied. The surface of the vapor-deposited aluminum film of the barrier / light-shielding layer formed in (4) above was superposed on the agent layer surface, and then both were dry-laminated and laminated. Next, the surface of the biaxially stretched nylon 6 film of the barrier / light-shielding layer laminated above was subjected to a corona discharge treatment, and the corona-treated surface was treated in the same manner as described above.
After that, a linear low-density polyethylene film having a thickness of 100 μm was dry-laminated on the surface of the above-mentioned laminating adhesive layer, and laminated to produce a laminated material. 8). (6). Next, using the above-mentioned laminated material, length, 170m
m, a front board made of 85 mm, and a rear board made of 85 mm, and simultaneously, a left board made of 170 mm, horizontal, and 60 mm, and a right board made, and the left board and the right board made Inserts a V-shaped fold inside, and then inserts left and right plates on the left and right sides of the front plate and the rear plate, and inserts the front plate, the rear plate, the left plate, and the right plate Heat seal the left and right ends, the lower end (oblique seal part and bottom seal part) of the outer periphery and the left and right end parts of the upper end to form a seal part. A gusset-type flexible packaging bag having an opening at the upper end was manufactured (see FIG. 2). (7). Next, first, the boat-shaped adhesive base of the spout body manufactured in the above (1) is brought into contact with the opening of the gusset-type soft packaging bag manufactured in the above (6), and the abutting part is ultrasonically irradiated. Heat sealing was carried out by a seal method and tightly adhered to produce a packaging container with a spout comprising the gusset-type soft packaging bag and the spout body. Next, soft drink water is filled and packaged through the opening of the spout of the packaging container with the spout, and the cap manufactured in the above (2) is screwed into the cylindrical opening at the opening. To produce a packaged product according to the present invention. (8). In the above packaging products, the packaging bag is heat resistant,
Excellent in pressure resistance, water resistance, barrier properties, heat sealability, pinhole resistance, piercing property, transparency, etc., and also excellent in barrier properties against oxygen gas, water vapor, etc. No leakage was observed, and it was excellent in the function as a food container, for example, suitability for filling and packaging the contents, suitability for distribution, and suitability for storage.

Embodiment 2 (1). In the same manner as in Example 1 above, using a polypropylene resin, the polypropylene resin is melted at about 200 ° C., and injection-molded using an injection molding method. Outer diameter, 14mm, height, 20m
m, and the boat-shaped adhesive base has a width of 20 m
A spout body consisting of m, height and 10 mm was manufactured (see FIG. 1). (2). In the same manner as in (1) above, a cap was formed by injection molding using a polypropylene resin and capable of being screwed onto the cylindrical mouth of the spout body. In addition, on the inner top surface of the above cap, a thickness 1 made of polyethylene sheet was used.
mm packing material was fitted and locked (FIG. 4). (3). 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 take-up type vacuum evaporation apparatus, and then unwound. Was used as a vapor deposition source, and while supplying oxygen gas, a 200-Å-thick aluminum oxide vapor-deposited film was formed 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: 420 m / min Evaporation surface : Corona-treated surface Next, immediately after forming the above-described 200-mm-thick aluminum oxide vapor-deposited film, a plasma output of 1500 W, oxygen gas was applied to the aluminum oxide-deposited film surface using a glow discharge plasma generator. (O ₂ ): argon gas (A
r) = 19: 1, a plasma treatment was performed with an oxygen / argon mixed gas at a mixed gas pressure of 6 × 10 ⁻⁵ Torr and a processing speed of 420 m / min to form a plasma treated surface. Next, an epoxy-based silane coupling agent (8.0% by weight) and an anti-blocking agent (1.0% by weight) were added to the polyurethane-based resin precondensate on the plasma-treated surface formed above, A sufficiently kneaded polyurethane-based resin composition is used, and is coated by a gravure roll coating method to a film thickness of 0.5 g / m ² (dry state), and then dried. Thus, a primer layer was formed to form a barrier layer. (4). A biaxially stretched nylon 6 film having a thickness of 15 μm was used, and this was fed out of a take-up type vacuum evaporation apparatus.
Then, it is fed out onto a coating drum, and on the corona treated surface, aluminum is used as a vapor deposition source under the following conditions, and an electron beam (EB) is used.
An aluminum vapor-deposited film having a thickness of 200 ° was formed by a vacuum vapor deposition method using a heating method. (Evaporation conditions) Evaporation source: Aluminum Degree of vacuum in vacuum chamber: 7.5 × 10 ⁻⁶ mbar Degree of vacuum in evaporation chamber: 2.1 × 10 ⁻⁶ mbar EB output: 20 KW Film transport speed: 600 m / Next, a 200-nm-thick aluminum vapor-deposited film was formed as described above to form a barrier / light-shielding layer. (5). Next, after forming a desired printed pattern on the surface of the primer agent layer of the barrier layer formed in the above (3), a two-part curable polyurethane laminate is applied over the entire surface including the printed pattern. The adhesive for coating is coated to a thickness of 4.0 g / m ² (dry state) by a gravure roll coating method to form an adhesive layer for laminating, and then the adhesive for laminating is applied. The surface of the vapor-deposited aluminum film of the barrier / light-shielding layer formed in (4) above was superposed on the agent layer surface, and then both were dry-laminated and laminated. Next, the surface of the biaxially stretched nylon 6 film of the barrier / light-shielding layer laminated above was subjected to a corona discharge treatment, and the corona-treated surface was treated in the same manner as described above.
After that, a linear low-density polyethylene film having a thickness of 100 μm was dry-laminated on the surface of the above-mentioned laminating adhesive layer, and laminated to produce a laminated material. 8). (6). Next, using the above-mentioned laminated material, using one laminated material, a front plate composed of a vertical, 170 mm, horizontal, 85 mm, and a rear plate, simultaneously, a vertical, 170 mm, a horizontal, 60 mm
mm to form a left side plate and a right side plate, and
The left side plate and the right side plate are engraved with a fold in a V-shape on the inside, and thereafter, the outer peripheral end and the lower end (diagonal sheet) where the end of the front plate and the end of the side plate overlap. And bottom sheet
), And heat sealing both the left and right ends of the upper end to form a seal portion, thereby producing a gusset-type flexible packaging bag having an opening at the upper end. (7). Next, using the gusset-type flexible packaging bag having an opening at the upper end manufactured in the above (6), first, in the same manner as in Example 1 above, first, the gusset-type soft packaging manufactured in the above (6) was used. The boat-shaped adhesive base of the spout body manufactured in the above (1) is brought into contact with the opening of the packaging bag, and the contacted part is heat-sealed by an ultrasonic seal method to tightly adhere. Thus, a packaging container with a spout comprising the gusset-type flexible packaging bag and the spout body was manufactured. Then, from the opening of the spout of the packaging container with the spout, filling and packaging soft drinks,
Further, the cap manufactured in the above (2) was screwed into the opening at the opening, thereby manufacturing a packaged product according to the present invention. (8). In the above packaging products, the packaging bag is heat resistant,
Excellent in pressure resistance, water resistance, barrier properties, heat sealability, pinhole resistance, piercing property, transparency, etc., and also excellent in barrier properties against oxygen gas, water vapor, etc. No leakage was observed, and it was excellent in the function as a food container, for example, suitability for filling and packaging the contents, suitability for distribution, and suitability for storage.

Comparative Example 1 (1). In the same manner as in Example 1 above, using a polypropylene resin, the polypropylene resin is melted at about 200 ° C., and injection molded using an injection molding method.
A spout body was manufactured having an inner diameter of 8.5 mm, an outer diameter of 11 mm, a height of 20 mm, and a boat-shaped adhesive base having a width of 20 mm, a height of 10 mm, and the like (see FIG. 1). (2). In the same manner as in (1) above, a cap was formed by injection molding using a polypropylene resin and capable of being screwed onto the cylindrical mouth of the spout body. In addition, on the inner top surface of the above cap, a thickness 1 made of polyethylene sheet was used.
mm packing material was fitted and locked (see FIG. 4). (3). On the other hand, on one surface of a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, a two-component curable polyurethane-based laminating adhesive having a thickness of 4.0 g / m ² (gravure roll coating) was used. (In a dry state) to form an adhesive layer for laminating, and then an aluminum foil having a thickness of 8 μm is superposed on the surface of the adhesive layer for laminating so as to face the adhesive layer. Were laminated by dry lamination. Next, a laminating adhesive layer is formed on the surface of the laminated aluminum foil in the same manner as described above, and then a 15 μm-thick biaxially stretched nylon is formed on the laminating adhesive layer surface. The six films were superposed facing each other, and then both were dry-laminated and laminated. Next, after applying a corona discharge treatment to the surface of the biaxially stretched nylon 6 film laminated as described above, an adhesive layer for laminating is formed on the corona treated surface in the same manner as described above. , On the surface of the laminating adhesive layer,
A 100 μm-thick linear low-density polyethylene film was dry-laminated and laminated to produce a laminated material. (4). Next, using the above-mentioned laminated material, length, 170m
m, a front board made of 85 mm, and a rear board made of 85 mm, and simultaneously, a left board made of 170 mm, horizontal, and 60 mm, and a right board made, and the left board and the right board made Inserts a fold into the inside of a V-shape, and then inserts a left side plate and a right side plate on both left and right sides of the front plate and the rear plate, and the front plate, the rear plate, the left side plate and the right side plate Heat seal the left and right ends, the lower end (oblique seal part and bottom seal part) of the outer periphery and the left and right end parts of the upper end to form a seal part. A gusset-type flexible packaging bag having an opening at the upper end was manufactured. (5). Next, first, the boat-shaped adhesive base of the spout body manufactured in the above (1) is brought into contact with the opening of the gusset-type soft packaging bag manufactured in the above (4). Heat sealing was carried out by a seal method and tightly adhered to produce a packaging container with a spout comprising the gusset-type soft packaging bag and the spout body. Next, soft drink water is filled and packaged through the opening of the spout of the packaging container with the spout, and the cap manufactured in the above (2) is screwed into the cylindrical opening at the opening. To produce a packaged product.

Comparative Example 2 (1). In the same manner as in Example 1 above, using a polypropylene resin, the polypropylene resin is melted at about 200 ° C., and injection molded using an injection molding method.
A spout body was manufactured having an inner diameter of 8.5 mm, an outer diameter of 11 mm, a height of 20 mm, and a boat-shaped adhesive base having a width of 20 mm, a height of 10 mm, and the like (see FIG. 1). (2). In the same manner as in (1) above, a cap was formed by injection molding using a polypropylene resin and capable of being screwed onto the cylindrical mouth of the spout body. In addition, on the inner top surface of the above cap, a thickness 1 made of polyethylene sheet was used.
mm packing material was fitted and locked (see FIG. 4). (3). On the other hand, on one surface of a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, a two-component curable polyurethane-based laminating adhesive having a thickness of 4.0 g / m ² (gravure roll coating) was used. (A dried state) to form an adhesive layer for laminating, and then a 15 μm-thick ethylene-vinyl alcohol copolymer film is superposed on the surface of the adhesive layer for laminating. Together
Thereafter, both were dry-laminated and laminated.
Next, an adhesive layer for laminating is formed on the surface of the ethylene-vinyl alcohol copolymer film laminated as described above in the same manner as described above. A biaxially stretched nylon 6 film having a thickness of 15 μm was superposed facing each other, and then both were dry-laminated and laminated. Next, after applying a corona discharge treatment to the surface of the biaxially stretched nylon 6 film laminated as described above, an adhesive layer for laminating is formed on the corona treated surface in the same manner as described above. Then, a linear low-density polyethylene film having a thickness of 100 μm was dry-laminated on the adhesive layer for laminating and laminated to produce a laminated material. (4). Next, using the above-mentioned laminated material, length, 170m
m, a front board made of 85 mm, and a rear board made of 85 mm, and simultaneously, a left board made of 170 mm, horizontal, and 60 mm, and a right board made, and the left board and the right board made Inserts a fold into the inside of a V-shape, and then inserts a left side plate and a right side plate on both left and right sides of the front plate and the rear plate, and the front plate, the rear plate, the left side plate and the right side plate Heat seal the left and right ends, the lower end (oblique seal part and bottom seal part) of the outer periphery and the left and right end parts of the upper end to form a seal part. A gusset-type flexible packaging bag having an opening at the upper end was manufactured. (5). Next, first, the boat-shaped adhesive base of the spout body manufactured in the above (1) is brought into contact with the opening of the gusset-type soft packaging bag manufactured in the above (4). Heat sealing was carried out by a seal method and tightly adhered to produce a packaging container with a spout comprising the gusset-type soft packaging bag and the spout body. Next, soft drink water is filled and packaged through the opening of the spout of the packaging container with the spout, and the cap manufactured in the above (2) is screwed into the cylindrical opening at the opening. To produce a packaged product.

EXPERIMENTAL EXAMPLES The laminates, bags with spouts and the like produced in Examples 1 and 2 and Comparative Examples 1 and 2 are described in (1). Oxygen permeability, (2). Water vapor permeability, (3). Seal strength,
(4). Light shielding properties, (5). Bending resistance, and (6).
Items for suitability for bag-making products were measured. (1). Measurement of Oxygen Permeability This is a condition of 23 ° C. and 90% RH in the United States.
The measurement was carried out using a measuring instrument (model name, OXTRAN) manufactured by MOCON. (2). Measurement of water vapor transmission rate This is the condition under the condition of temperature 40 ° C and humidity 90% RH,
The measurement was carried out with a measuring device (model name, PERMATRAN) manufactured by MOCON. (3). Measurement of seal strength This is to seal the sample 15 mm
Strip width, T-peel with Tensilon, peeling speed 3
The measurement was performed at 00 mm / min with a knob spacing of 50 mm. (4). This is a color computer manufactured by Suga Test Instruments Co., Ltd.
And the total light transmittance (%) was measured and evaluated. (5). Measurement of flex resistance This was measured by measuring the number of pinholes after bending 2000 times with a Gelbo tester under the condition of -3 ° C. (6). Measurement of suitability for bag-making products (6) -1. Drop test This was measured by dropping vertically from a height of 1.5 m and counting the number of times to break the bag. In addition, the content used water, and it ended by 30 times. (6) -2. Sensory test: This was measured by storing in a 60 ° C. oven for 7 days and evaluating whether there was no change in the taste of the contents or smell.
Indicates that there is no change in both taste and smell, and x indicates that there is some change in taste and smell. The contents used water. (6) -3. Storage test This is performed using a xenon lamp weather meter.
After storage for a week, the contents were evaluated for discoloration and measured. The contents used were jelly. The test results are shown in Table 1 below.

[0059] 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. · 90% RH].
H], and the unit of the seal strength is [kgf / 15m
m], the unit of the total light transmittance is [%], and the unit of the number of pinholes is [pcs / A4size].

As is clear from the measurement results shown in Table 1 above, it was confirmed that the samples according to Examples 1 and 2 were excellent in all items and had sufficient practicality. On the other hand, it was confirmed that Comparative Examples 1 and 2 were inferior in a few items.

[0061]

As is apparent from the above description, the present invention firstly manufactures a spout body comprising a cylindrical mouth and a boat-shaped adhesive base connected below the cylindrical mouth. , At least, a barrier layer provided with an inorganic oxide deposited film and a primer agent layer on one surface of the base film, and a barrier and light-shielding property provided with a metal deposited film on one surface of the base film Using a laminated material obtained by sequentially laminating layers and heat-sealing resin layers, a bag-shaped container main body constituting a plastic free-packing bag such as a self-supporting bag or a casset-type bag is formed. Then, the boat-shaped adhesive base constituting the spout body is brought into contact with the opening on one side of the bag-shaped container body,
The two are fixed at the contact portion with a heat seal or the like to produce a spout-equipped bag comprising the above-described spout body and the bag-shaped container body, and thereafter, the spout-equipped bag. The contents are filled in the inside, and further, a cap or the like that seals the opening is screwed to the cylindrical mouth portion of the spout body constituting the bag with the spout via a screw portion or the like, so that the packaged product is It has excellent physical properties such as heat resistance, pressure resistance, water resistance, heat sealability, pinhole resistance, puncture resistance, light shielding properties, etc. It has excellent barrier properties to prevent permeation, and also withstands heat treatment accompanying processing such as boil treatment, and also reduces the amount of container and packaging waste and shortens the manufacturing process, thereby reducing the manufacturing cost. For example, juices, fruit juices, jelly-like beverages, nutritional drinks It is a useful packaging container for filling and packaging foods and drinks such as drinking water, tea, coffee drinks, milk, seasonings, oils, and others. Can be manufactured.

[Brief description of the drawings]

FIG. 1 is a schematic perspective view showing one example of a spout main body constituting a bag with a spout according to the present invention.

FIG. 2 is a schematic perspective view showing an example of a bag-shaped container main body constituting a bag with a spout according to the present invention.

FIG. 3 is a schematic perspective view showing an example of a bag with a spout according to the present invention.

FIG. 4 is a schematic perspective view showing an example of a cap attached to a cylindrical mouth of a spout main body constituting a spout-equipped bag according to the present invention.

FIG. 5 is a schematic perspective view showing an example of a cap attached to a cylindrical mouth portion of a spout main body constituting a spout-equipped bag according to the present invention.

FIG. 6 is a schematic perspective view showing an example of a spout main body having another form with respect to a spout main body constituting a bag with a spout according to the present invention.

FIG. 7 is a schematic perspective view showing an example of a spout body having another form with respect to the spout body constituting the bag with a spout according to the present invention.

FIG. 8 is a schematic cross-sectional view showing an example of a laminated material forming a bag-shaped container main body constituting a bag with a spout according to the present invention.

FIG. 9 is a schematic configuration diagram showing an outline of an example of a take-up type vacuum evaporation apparatus.

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

[Explanation of symbols]

 Reference Signs List A A spouted bag B Spout main body C Bag-shaped container main body D Cap E Laminate 1 Cylindrical mouth 2 Boat-shaped adhesive base 3 Screw 4 Intermediate ring 5 Large-diameter cylindrical 6 Flange 11 Front plate 12 Back plate 13, 14 Side plate 15 Seal portion 16 Opening 41, 41a Base film 42 Deposited film of inorganic oxide 43 Primer agent layer 44 Barrier layer 45 Deposited film of metal 46 Barrier and light-shielding layer 47 Heat-sealing resin layer

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B32B 9/00 B32B 9/00 A 15/08 15/08 F B65D 33/36 B65D 33/36 C23C 14 / 08 C23C 14/08 A 16/42 16/42 F term (reference) 3E064 AA13 AB13 AB14 BA17 BA24 BA36 BA54 BB03 BC01 BC08 BC18 EA08 EA12 EA18 FA03 GA01 HM01 HN65 4D075 AE19 BB49X BB85Y CA12 CA18 CA38 CA41 CB07 DC04 EA41 EB01 EB12 EB13 EB22 EB35 EB38 EC45 4F100 AA17B AA19B AA20B AB01C AB10C AH06B AK01A AK01D AK03D AK41G AK51B AK51G AL05B AL05G AT00A BA04 BA07 BA10B BA10D BA13 CA23B CC00B DA01 DA04 EH46B EH66B EH66C EJ38A EJ65B EJ67B GB17 GB23 JB07 JD02B JD02C JD03 JD04 JJ03 JK05 JK14 JK20 JL02 JL12D JN02C 4K029 AA11 BA44 BC00 BD06 CA02 GA02 JA10 KA03 4K030 AA06 AA14 BA44 CA07 CA12 DA08 FA01 GA14 LA24

Claims (12)

[Claims] 1. A spout main body comprising a cylindrical mouth and a boat-shaped adhesive base connected below the cylindrical mouth, and a bag-shaped container main body fixed to the boat-shaped adhesive base constituting the spout main body. Further, the bag-shaped container body, at least, a barrier layer provided with an inorganic oxide deposited film and a primer agent layer on one surface of the substrate film, one surface of the substrate film A barrier / light-shielding layer provided with a metal vapor-deposited film, and
A bag with a spout, characterized in that the bag is made from a laminated material in which a heat-sealing resin layer is sequentially laminated. 2. A spout-equipped outlet according to claim 1, wherein a closure-preventing member for preventing the bag-shaped container main body from being obstructed is connected below the boat-shaped adhesive base constituting the spout main body. bag. 3. The bag according to claim 1, wherein the bag-shaped container body is a self-supporting bag or a gusset-type bag.
Bag with spout described in. 4. A bag with a spout according to any one of claims 1 to 3, wherein a cap is attached to a cylindrical mouth portion forming the spout body. 5. The bag with a spout according to claim 1, wherein the base film comprises a biaxially stretched resin film or sheet. 6. A spout according to claim 1, wherein the deposited film of the inorganic oxide comprises a deposited film of the inorganic oxide formed by physical vapor deposition or chemical vapor deposition. bag. 7. The bag with a spout according to claim 1, wherein the inorganic oxide vapor-deposited film comprises an aluminum oxide vapor-deposited film formed by physical vapor deposition. 8. The bag with a spout according to claim 1, wherein the deposited film of the inorganic oxide comprises a deposited film of silicon oxide formed by chemical vapor deposition. 9. The method according to claim 1, wherein the primer agent layer comprises a coating film made of a resin composition containing a polyurethane resin or a polyester resin as a main component of the vehicle. Bag with spout. 10. A primer agent layer comprising a polyurethane-based resin or a polyester-based resin as a main component of a vehicle,
The bag with a spout according to any one of claims 1 to 9, further comprising a coating film made of a resin composition containing a silane coupling agent and a filler. 11. The bag with a spout according to claim 1, wherein the metal vapor-deposited film comprises an aluminum vapor-deposited film. 12. The method according to claim 1, wherein the heat-sealing resin layer comprises a polyolefin resin layer.
12. The liquid paper container according to any one of items 11 to 11.