JP7196442B2 - laminate - Google Patents

Description

TECHNICAL FIELD The present invention relates to a laminate for packaging bags that uses a laminated packaging material having oxygen barrier properties and ultraviolet shielding properties and is less likely to cause pinholes when a thick and heavy object is packed and transported. The present invention also relates to a laminate suitable for a packaging bag used for packaging contents whose quality is easily deteriorated by the intrusion of oxygen or ultraviolet rays in the field of foodstuffs and the like.

Glass bottles, which have traditionally been used as filling containers for medical solutions, have problems such as being heavy, risking breakage due to impact, and being bulky, making transportation and storage inconvenient. Instead, soft bags or bag-like containers made of plastic materials such as polyethylene resin, polypropylene resin, and polyvinyl chloride resin are often used.

Such a container is often filled in a flexible plastic primary container as disclosed in Patent Document 1, for example, from the viewpoint of ease of handling, weight reduction of the container, and reduction of the volume of waste. many.

Among the liquids filled in such containers, especially chemical liquids such as amino acid liquids, sugars, and electrolyte liquids are significantly degraded by oxygen, and many vitamins are easily degraded by near-ultraviolet rays.

On the other hand, since these drug solutions may be directly injected into the body, the bag-like container that comes into direct contact with these drug solutions should be kept in a non-toxic state so that the components eluted from the container itself do not adversely affect the drug solution. Containers with additive plastics are often used.

However, in a container using additive-free plastic, it is difficult to ensure high oxygen barrier properties and UV shielding properties that can prevent the chemical solution from deteriorating and deteriorating as described above.

Therefore, in recent years, secondary packaging of a primary container in which a chemical solution is filled and sealed has been carried out in an exterior bag having a high barrier property.

As the barrier layer having oxygen barrier properties and UV shielding properties as described above, for example, metal foil can be exemplified. The bag is inevitably harder than other types, making it difficult to handle depending on the application, and it is also expensive.

On the other hand, there is an idea to use a metal vapor deposition film, but a general metal vapor deposition film is relatively easy to damage because the metal vapor deposition film is easily damaged due to contact with a roll during the processing process. In many cases, a difficult dry lamination method is used.

However, when the dry lamination method is used, the film thickness of the adhesive layer is thin, and a reinforcing layer is often required in order to suppress the generation of pinholes due to impact during transportation.

Among them, as in Patent Document 2, a barrier layer, which is a co-extruded co-stretched film composed of a nylon layer/ethylene-vinyl alcohol copolymer layer/nylon layer, and a metallized film are dry-laminated in advance to form an aluminum film. A so-called sandwich lamination method has also been proposed, in which, after protecting the layers, the outermost layer and the innermost layer are laminated via an extruded resin to the previously dry-laminated film.

JP-A-10-314272 Japanese Patent Application Laid-Open No. 2004-050605

In view of such circumstances, the present invention uses a metal-deposited film as an oxygen barrier layer and an ultraviolet shielding layer, and produces a laminate that can provide an outer bag for chemical solutions at low cost without using an additional reinforcing layer. I am trying to.

The present invention has been made to solve these problems.
That is, the invention according to claim 1 is a laminate obtained by laminating a substrate film, a metallized film, and a sealant film in at least this order from the outside with an extruded resin layer interposed therebetween,
An anchor coating agent layer is provided on the metal-deposited surface side of the metal-deposited film, and the oxygen permeability of the sealant film is 0.8 cc/m 2 ^day -atm or less,
A laminate comprising the anchor coating agent layer and the sealant film has an oxygen permeability of 1.0 cc/m ² ·day·atm or less .

The invention according to claim 2 is the laminate according to claim 1, wherein the sealing strength when the sealant films are heat-sealed to each other is 50 N/15 mm or more.

The invention according to claim 3 is characterized in that the sealant film is a coextruded film in which a linear low-density polyethylene resin is laminated on both front and back surfaces of an ethylene-vinyl alcohol copolymer. A laminate according to claim 2 .

The invention according to claim 4 is the laminate according to any one of claims 1 to 3, wherein the anchor coating agent layer contains an inorganic layered mineral.

According to the present invention, it is possible to provide an extruded laminated laminate that can be used as an outer bag for chemical liquids without the need for an additional reinforcing layer while using a metallized film as a barrier layer and an ultraviolet shielding layer.

FIG. 2 is a cross-sectional view showing a structural example of a laminate of the present invention; FIG. 4 is a cross-sectional view showing an example of a metal-deposited film and an anchor coating agent layer; It is sectional drawing which shows the structural example of a sealant film.

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below. Although the drawings will be referred to in the following description as appropriate, the aspects described in the drawings are examples of the present invention, and the present invention is not limited to the aspects described in these drawings.

In addition, throughout all the drawings, the same reference numerals are given to constituent elements exhibiting the same or similar functions, and redundant explanations are omitted.

FIG. 1 is a cross-sectional view showing a configuration example of the laminate of the present invention.

FIG. 1 shows each layer of a substrate film (11), a metal-deposited film (14) provided with an oxygen-barrier anchor coating agent layer (13) on the metal-deposited surface, and a sealant film (15) having oxygen-barrier properties. is laminated via an extruded resin layer (12).

Although the oxygen barrier sealant film (15) is shown as a single layer in FIG. 1, it is actually formed of multiple layers of coextruded films, which will be described later.

Here, as the base film (11), any conventionally known film can be used. - Nylon, polyamide films such as polymetaxylylene adipamide (MXD6), polycarbonate films, polyacrylonitrile films, polyimide films, polyvinyl alcohol films, polyvinylidene chloride films, etc., which have mechanical strength and dimensional stability It is not particularly limited as long as it is a substance. A stretched film is particularly preferable, and a stretched polypropylene (OPP) film or the like can be preferably used in consideration of cost and ease of handling.

The thickness of the substrate film is preferably in the range of 10 to 50 μm in consideration of workability.

In addition, a printed layer or the like can be appropriately provided on the base film (11) as necessary. As the printing layer, various pigments, extender pigments, plasticizers, desiccants, stabilizers, surfactants, etc. are optionally added to conventionally known binder resins such as urethane, acrylic, nitrocellulose, and rubber. It can be configured using ink or the like.

As a printing method, conventionally known methods such as offset printing, gravure printing, flexographic printing, silk screen printing, and inkjet printing can be arbitrarily used.

Further, the surface of the base film (11) may be subjected to an easy-adhesion treatment such as corona treatment or ozone treatment.

As shown in FIG. 2, the metal vapor deposition film (14) has a metal vapor deposition film (142) provided on a vapor deposition film substrate (141). An agent layer (13) is laminated.

In addition, on the side of the deposited film substrate (141) on which the metal deposition film (142) is not provided, an anchor coating agent layer (13) having oxygen barrier properties, an adhesive layer having no particular oxygen barrier properties, or the like is applied. may be provided separately.

As the deposited film substrate (141), for example, a polyester film such as polyethylene terephthalate, a polyolefin film such as polypropylene, a nylon film, an ethylene-vinyl alcohol copolymer film, or the like can be used.

Among them, a stretched polyethylene terephthalate (PET) film can be preferably used in consideration of mechanical strength, ease of handling, and the like.

The thickness of the deposited film substrate (141) can be about 3 to 200 μm, more preferably 6 to 50 μm.

The vapor-deposited metal film (142) is provided for the purpose of imparting oxygen barrier properties and shielding against ultraviolet rays. Chromium, iron, nickel and the like can be exemplified, and aluminum can be preferably used.

Regarding the oxygen barrier property of the metal vapor deposited film (14) having the metal vapor deposited film (142), the oxygen permeability according to JIS K7126 is 1.0 cc/m ² · day · atm (temperature 22 ° C., humidity 65% RH conditions ) should be less than

As for the ultraviolet shielding property of the metal deposited film (14), it is desirable that the light transmittance of SZ-Σ80 manufactured by Nippon Denshoku Industries Co., Ltd. is 0.1% or less.

The film thickness of the vapor-deposited metal film (142) as described above can be in the range of about 5 to 300 nm, and more preferably in the range of 10 to 100 nm.

As a method for forming the metal deposited film (142), any known thin film forming method may be used, for example, physical vapor deposition methods such as vacuum deposition, sputtering, and ion plating. etc. can be exemplified.

Prior to the formation of the metal vapor deposition film (142), the surface of the vapor deposition film substrate (141) may be subjected to surface treatment such as corona treatment, plasma treatment, or ion bombardment treatment.

In the case of using the above-described metal-deposited film (14) as an oxygen barrier layer, in the post-processing step for the metal-deposited film, the metal-deposited surface of the metal-deposited film (14) is placed in the transport path of the apparatus. When the metal vapor deposition film (14) is unwound from the rolled metal vapor deposition film (14), the metal vapor deposition film (142) is rubbed against the metal vapor deposition film (142) due to rubbing against the metal vapor deposition film substrate (141) on the back surface. Partial lack occurred, and the oxygen barrier property originally possessed by the metallized film (14) was sometimes impaired.

In response to such problems, the present inventors have developed a layer structure capable of compensating for the reduced oxygen barrier property even when the metal deposition film (142) is partially missing as described above. As a result, the inventors have found a method of making a laminate that can be used as an exterior bag for a chemical solution without using an additional reinforcing layer.

That is, an anchor coating agent layer (13) having oxygen barrier properties is provided on the metal vapor deposition film (142) side of the metal vapor deposition film (14), and a film having oxygen barrier properties is used as the sealant film (15). It is.

Such an anchor coating agent layer (13) contains, as a main agent, for example, solvent-soluble or water-soluble polyester resin, isocyanate resin, urethane resin, acrylic resin, polyvinyl alcohol resin, ethylene vinyl alcohol resin, vinyl-modified resin, epoxy resin. Resins, imine resins, oxazoline group-containing resins, modified styrene resins, modified silicone resins, alkyl titanates, and the like can be used, and these can be used alone or in combination of two or more.

Various additives such as curing agents, catalysts, stabilizers and initiators can be added to the anchor coating agent layer (13) depending on the resin used.

As a method for imparting oxygen barrier properties to the anchor coat agent layer (13), any conventionally known method can be used, and for example, a method of adding an inorganic layered mineral or the like can be exemplified.

Inorganic layered minerals are inorganic compounds in which ultra-thin unit crystal layers are superimposed to form a single layered particle. Preferred inorganic layered minerals are those that swell and cleave in water. In particular, a clay compound having a property of swelling in water is preferably used, and the clay compound may be natural or synthetic.

Representative examples of inorganic layered minerals include hydrous silicates such as phyllosilicate minerals, and kaolinite-serpentinite clays such as halloysite, kaolinite, enderite, dikite, nacrite, antigorite, and chrysotile. Minerals, smectite group clay minerals such as montmorillonite, beidellite, nontronite, saponite, hectorite, sauconite, stevensite, vermiculite group clay minerals such as vermiculite, mica such as muscovite, phlogopite, siderophyllite, margarite, tetrasilic Examples include mica, teniolite, and other mica or mica group clay minerals.

These inorganic layered minerals can be used singly or in combination of two or more.

The thickness of the anchor coating agent layer (13) imparted with oxygen barrier properties by adding the above inorganic layered minerals or the like is about 3.0 to 5.0 g/m ² in terms of coating amount after drying. is desirable.

If the coating amount after drying is less than 3.0 g/m ² , it may be insufficient to compensate for the reduced oxygen barrier properties of the metal vapor deposition film, and if it exceeds 5.0 g/m ² , the coating amount becomes excessive compared to the oxygen barrier effect, which is disadvantageous in terms of cost.

In order to improve the applicability and adhesiveness of the anchor coating agent layer (13), the surface of the metallized film (14) may be subjected to corona treatment prior to formation of the anchor coating agent layer.

Such an anchor coating agent layer (13) can be provided using a conventionally known coating method, and examples thereof include gravure coating, micro gravure coating, roll coating, and die coating. Among them, the gravure coating method can be preferably used.

FIG. 3 is a cross-sectional view showing a configuration example of a sealant film (15) having oxygen barrier properties.

Any film can be used as the sealant film (15) as long as it is heat-sealable and has oxygen barrier properties. A co-extruded film having a sandwich-like laminate structure flanked by layers of sealant material (152) can be suitably used.

For the oxygen barrier resin layer (151), any conventionally known resin having oxygen barrier properties can be used. , ethylene-vinyl alcohol copolymer (EVOH), and the like.

Among such oxygen barrier resins, ethylene-vinyl alcohol copolymer (EVOH) can be suitably used, and the thickness can be about 1 to 10 μm.

In addition, the sealant material layer (152) can use polyolefin-based resin, specifically, low density polyethylene resin (LDPE), linear low density polyethylene resin (LLDPE), medium density polyethylene resin (MDPE). , high density polyethylene resin (HDPE), polypropylene resin (PP), ethylene-propylene copolymer (EP), ethylene-α olefin copolymer, ethylene-methacrylic acid copolymer (EMAA), ethylene-acrylic acid copolymer Examples include coalesced (EAA), ethylene-vinyl acetate copolymer (EVA), ionomer resins, and the like.

Among them, linear low-density polyethylene resin (LLDPE) can be preferably used, and the thickness can be about 10 to 30 μm.

The sealant film (15) as described above has an oxygen permeability according to JIS K7126 of 0.8 cc/m ² ·day · atm (temperature 22 ° C., humidity 65% RH conditions) or less, and the sealant films are separated from each other. It is desirable that the seal strength when heat-sealed is 50 N/15 mm or more.

In the sealant film (15), an adhesive layer or the like may be provided between the oxygen barrier resin layer (151) and the sealant material layer (152).

By using such a sealant film (15), the vapor-deposited metal film (142) of the vapor-deposited metal film (14) is partially missing, and the original oxygen barrier property of the vapor-deposited metal film (14) is impaired. Even in this case, it is possible to supplement the oxygen barrier properties of the laminate (1).

Moreover, even when used as an outer bag for a heavy object such as a primary container filled with a chemical solution, it has sufficient sealing strength to provide a safe outer bag that does not break easily due to its sufficient sealing strength. becomes possible.

Each layer of the substrate film (11), the metallized film (14) including the anchor coating agent layer (13), and the sealant film (15) as described above is laminated via the extruded resin layer (12) by a sandwich lamination method. are laminated together.

The extruded resin layer (12) can use commonly available extruded resins such as low-density polyethylene resin (LDPE), medium-density polyethylene resin (MDPE), linear low-density polyethylene resin ( LLDPE), polypropylene resin (PP), ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl alcohol copolymer (EVOH), ionomer, ethylene-methacrylic acid copolymer (EMAA), or ethylene -Acrylic acid copolymer (EAA), ethylene-acrylate copolymer (EEA), etc. can be used.

The thickness of the extruded resin layer is desirably about 10 to 30 μm. Thus, by using the sandwich lamination method using an extruded resin layer, it is possible to provide a thicker resin layer than in the dry lamination method in which adhesive resin is coated and laminated.

Therefore, even without providing a reinforcing layer, etc., which is required when using the dry lamination method, the outer packaging for the chemical solution does not cause pinholes even when the primary packaging bag filled with the chemical solution is sealed, and the impact during the transportation work does not occur. It can be a laminate that can provide a bag.

The examples shown below are only examples, and the present invention is not necessarily limited to the examples shown below.

<Example 1>
As shown below, a laminate sample 1 was produced by laminating a metal-deposited film and a sealant film in this order by a sandwich lamination method, using polypropylene as a surface layer base film.

At that time, an anchor coating agent layer shown below was provided on the metal deposition surface side of the metal deposition film as an anchor coating agent layer having an oxygen barrier property.

The heat seal strength between the sealant films of the obtained laminate was 54 N/15 mm.

(Base film)
Oriented propylene film (OPP): FOS 50 μm manufactured by Futamura Chemical Co., Ltd.
(metal deposition film)
PET film with aluminum vapor deposition … Manufactured by Oike Pack Material Co., Ltd.
JC-V8 12 μm
(sealant film)
Co-extruded film (LLDPE/EVOH/LLDPE) … manufactured by Tamapoly Co., Ltd.
Multitron (registered trademark) ZEA-101 60 μm
(Oxygen permeability: 0.5 cc/m ² ·day · atm)
(Extruded resin layer)
Low-density polyethylene (LDPE): manufactured by Japan Polyethylene Co., Ltd.
LC600A 20 μm
(Anchor coating agent layer)
Two-liquid curing type polyester polyol … manufactured by DIC Corporation
PASLIM VM001 4.8 μm

<Comparative Example 1>
A laminate sample 2 was produced in the same manner as in Example 1, except that an LLDPE film (Elsmart (registered trademark) manufactured by Mitsui Chemicals Tohcello, Inc.) having no oxygen barrier properties was used as the sealant film.

<Comparative Example 2>
Laminate sample 3 was produced in the same manner as in Example 1, except that a urethane-based material (A3210, manufactured by Mitsui Chemicals, Inc.) having no oxygen barrier properties was used as the anchor coat agent layer.

<Comparative Example 3>
A urethane-based material (A3210, manufactured by Mitsui Chemicals, Inc.) that does not have oxygen barrier properties is used as the anchor coating agent layer, and LLDPE (Lsmart (registered trademark), Mitsui Chemicals Tohcello, Inc.) that does not have oxygen barrier properties is used as the sealant film. A laminate sample 4 was prepared in the same manner as in Example 1, except that ) was used.

Two types of evaluation, Experiment 1 and Experiment 2, shown below were carried out for each laminate sample produced as described above.

<Experiment 1>
Laminate samples 1 to 4 prepared in Example 1, Comparative Example 1, Comparative Example 2, and Comparative Example 3, and the pre-processed metal vapor deposition film used in each sample were measured at a temperature of 22° C. and a humidity of 65% RH. The oxygen permeability was measured according to JIS K7126 under the conditions, and the measurement results are shown in Table 1.

From the results of Example 1 and Comparative Examples 1 to 3, the effect of compensating for the deterioration of the oxygen barrier properties due to the processing steps during the production of the laminate by using those having oxygen barrier properties for the anchor coating agent layer and the sealant film was demonstrated. found to have.

Further, from the results of Comparative Examples 1 and 2, under the conditions of a temperature of 22° C. and a humidity of 65% RH, rather than only the anchor coating agent layer having oxygen barrier properties, only the sealant film It was found that the deterioration of the oxygen barrier property can be compensated for in the case of having the oxygen barrier property.

<Experiment 2>
From the results of Experiment 1, each laminate sample of Example 1, Comparative Example 1, and Comparative Example 2, in which it was confirmed that the effect of compensating for the deterioration of the oxygen barrier property in the processing process at the time of laminate production was measured at a temperature of 40° C. and a humidity of 70° C. % RH in a high-temperature and high-humidity environment was measured in the same manner as in Experiment 1, and the measured results are shown in Table 2.

From the results of Comparative Examples 1 and 2, when only one of the anchor coat layer and the sealant film has the oxygen barrier property, the temperature is 22° C. and the humidity is 65% RH. Even if the oxygen barrier property can be maintained to some extent, in a high-temperature and high-humidity environment with a temperature of 40°C and a humidity of 70% RH, the oxygen permeability is around 1.0 cc/m ² ·day · atm or more. It can be seen that it shows

A value of 1.0 cc/m ² ·day·atm or less is required in the case of an outer bag for containing a primary container filled with a medical solution, etc., which is shown in Comparative Examples 1 and 2. Such a configuration cannot withstand the intended use.

On the other hand, it was found that by adopting the structure of the laminate shown in Example 1, it is possible to ensure stable oxygen barrier properties even in a high-temperature and high-humidity environment.

From the above results, by using the laminate of the present invention, it has sufficient characteristics as an outer bag for a primary container filled with a chemical solution, and an additional reinforcing layer for satisfying oxygen barrier properties etc. It is possible to provide an inexpensive laminate for exterior bags without using it.

DESCRIPTION OF SYMBOLS 10... Laminate 11... Base film 12... Extruded resin layer 13... Anchor coating agent layer 14... Metal vapor deposition film 141... Vapor deposition film substrate 142... Metal vapor deposition film 15... Sealant film 151... Gas barrier resin layer 152... Sealant material layer

Claims (4)

A laminate obtained by laminating a substrate film, a metallized film, and a sealant film in at least this order from the outside with an extruded resin layer interposed therebetween,
An anchor coating agent layer is provided on the metal-deposited surface side of the metal-deposited film,
The oxygen permeability of the sealant film is 0.8 cc/m ² ·day · atm or less,
A laminate comprising the anchor coating agent layer and the sealant film having an oxygen permeability of 1.0 cc/m ² ·day·atm or less. 2. The laminate according to claim 1, wherein the sealing strength when the sealant films are heat-sealed to each other is 50 N/15 mm or more. 3. The laminate according to claim 1, wherein the sealant film is a coextruded film obtained by laminating linear low-density polyethylene resin on both sides of the ethylene-vinyl alcohol copolymer. 4. The laminate according to any one of claims 1 to 3, wherein the anchor coating agent layer contains an inorganic layered mineral.

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