JP2020011390A - Laminate - Google Patents

Abstract

To provide a laminate capable of inexpensively manufacturing an exterior bag for chemical fluid while using a metal vapor deposition film as an oxygen barrier layer and an ultraviolet ray shielding layer without using an additional reinforcement layer.SOLUTION: The laminate is formed by laminating a base material film 11, a metal vapor deposition film 14, and a sealant film 15 at least in this order from outside through an extrusion resin layer 12. In the laminate, an anchor coating agent layer 13 is provided at the side of a metal vapor deposition surface of the metal vapor deposition film and the anchor coating agent layer and the sealant film are formed to have oxygen barrier properties.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a laminated body for a packaging bag, which hardly generates pinholes when packing and transporting a thick and heavy object using a laminated packaging material having an oxygen barrier property and an ultraviolet shielding property, and is used for medical and pharmaceutical products. Also, the present invention relates to a laminate suitable for a packaging bag used for packaging contents whose quality is easily degraded by invasion of oxygen or ultraviolet rays in the field of foods and the like.

  Glass bottles that have been conventionally used as filling containers for medical liquids are heavy, have the risk of being damaged by impact, and are bulky and have problems such as inconvenience in transportation and storage. Instead, a soft bag or bag-like container made of a plastic material such as a polyethylene resin, a polypropylene resin, and a polyvinyl chloride resin is often used.

  Such a container may be filled in a flexible plastic primary container as disclosed in Patent Document 1, for example, from the viewpoint of good handling (handling), lightening of the container, and reduction of the volume of dust. Many.

  Among the contents liquids filled in such containers, especially chemical solutions such as amino acid solutions, sugars and electrolyte solutions are remarkably deteriorated by oxygen, and vitamins are easily deteriorated by near ultraviolet rays in many cases.

  On the other hand, since these chemicals may be directly injected into the body, a bag-shaped container that comes into direct contact with these chemicals should be used without dissolving components from the container itself so as not to adversely affect the chemicals. Containers using added plastic are often used.

  However, it is difficult to guarantee a high oxygen barrier property and a high ultraviolet ray shielding property in a container using an additive-free plastic so as to prevent the chemical solution from being deteriorated or deteriorated as described above.

  Therefore, in recent years, a primary container, which is filled and sealed with a chemical solution, is secondarily packaged with an outer bag having a high barrier property.

  Examples of the barrier layer having the oxygen barrier property and the ultraviolet ray shielding property as described above include a metal foil, for example. When the metal foil is laminated with a plastic film, the barrier effect is excellent, but the plastic bag is excellent. It is inevitable that the bag becomes harder than the type, and there are difficulties in handling depending on the use, and the price is expensive.

  On the other hand, although there is a concept of using a metal vapor-deposited film, in a general metal vapor-deposited film, the metal vapor-deposited film may be easily damaged due to contact with a roll or the like in a processing step, and relatively scratches are generated. In many cases, a difficult dry lamination method is used.

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

As described in Patent Document 2, a barrier layer, which is a co-pressed co-stretched film composed of a nylon layer / ethylene-vinyl alcohol copolymer layer / nylon layer, and a metal-deposited film are dry-laminated in advance, A so-called sandwich lamination method in which the outermost layer and the innermost layer are laminated through an extruded resin with respect to the previously dry-laminated film after the layer is protected has also been proposed.

JP-A-10-314272 JP 2004-050605 A

  In view of such circumstances, the present invention provides a laminate that can provide an outer bag for a chemical solution at low cost without using an additional reinforcing layer while using a metal-deposited film as an oxygen barrier layer and an ultraviolet shielding layer. What you want to do.

The present invention has been made to solve these problems.
That is, the invention according to claim 1 is a laminate in which a base film, a metal-deposited film, and a sealant film are laminated at least in this order via an extruded resin layer from the outside, and the metal of the metal-deposited film is On the deposition surface side, an anchor coat agent layer is provided,
The laminate, wherein the anchor coat agent layer and the sealant film have oxygen barrier properties.

In the invention according to claim 2, the sealant film has an oxygen permeability of 0.8 cc / m ² · day · atm or less, and has a seal strength of 50 N / when the sealant films are heat-sealed to each other. The laminate according to claim 1, wherein the thickness is 15 mm or more.

  The invention according to claim 3 is characterized in that the sealant film is a co-extruded film in which a linear low-density polyethylene resin is laminated on both 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 coat agent layer contains an inorganic layered mineral.

  ADVANTAGE OF THE INVENTION According to this invention, while using a metal vapor deposition film as a barrier layer and an ultraviolet-ray shielding layer, it does not require an additional reinforcement layer, and it becomes possible to provide the extrusion laminated laminate which can be used as an outer bag for chemicals.

It is sectional drawing which shows the structural example of the laminated body of this invention. It is sectional drawing which shows the example of a metal vapor deposition film and an anchor coat agent layer. It is sectional drawing which shows the structural example of a sealant film.

  Hereinafter, embodiments of the present invention will be described in detail. In the following description, reference is made to the drawings as appropriate, but the embodiments described in the drawings are exemplifications of the present invention, and the present invention is not limited to the embodiments described in these drawings.

  Note that, throughout all the drawings, components that perform the same or similar functions are denoted by the same reference numerals, and redundant description will be omitted.

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

  FIG. 1 shows each of a base film (11), a metal vapor-deposited film (14) provided with an anchor coat agent layer (13) having an oxygen barrier property on a metal vapor-deposited surface, and a sealant film (15) having an oxygen barrier property. However, there is shown a configuration example in which is laminated via an extruded resin layer (12).

  In FIG. 1, the sealant film (15) having an oxygen barrier property is shown as a single layer, but is actually formed by a multilayer coextruded film described later.

  Here, as the base film (11), any of conventionally known films can be used. For example, polyester films such as polyethylene terephthalate film and polyethylene naphthalate film, polyolefin films such as polypropylene, polystyrene films, -Polyamide films such as nylon and polymethaxylylene adipamide (MXD6), polycarbonate films, polyacrylonitrile films, polyimide films, polyvinyl alcohol films, polyvinylidene chloride films, etc., but have mechanical strength and dimensional stability. If it is a thing, it will not be specifically limited. In particular, a stretched film or the like is preferable, and in consideration of cost and ease of handling, a stretched polypropylene (OPP) film or the like can be suitably used.

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

  The base film (11) may be provided with a printing layer or the like as needed. As the print layer, various pigments, extenders and plasticizers, drying agents, stabilizers, surfactants, and the like are arbitrarily 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, for example, a conventionally known method such as offset printing, gravure printing, flexo printing, silk screen printing, or ink jet printing can be arbitrarily used.

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

  As shown in FIG. 2, the metal-deposited film (14) has a metal-deposited film (142) provided on a vapor-deposited film substrate (141), and at least an anchor coat is provided on the metal-deposited film (142). The agent layer (13) is laminated.

  On the side of the vapor-deposited film substrate (141) on which the metal vapor-deposited film (142) is not provided, an anchor coat agent layer (13) having an oxygen barrier property, an adhesive layer having no particular oxygen barrier property, or the like. May be provided separately.

  As the vapor deposition 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.

  Above all, a stretched polyethylene terephthalate (PET) film can be suitably used in consideration of mechanical strength, ease of handling, and the like.

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

  The metal vapor-deposited film (142) is provided for the purpose of providing oxygen barrier properties and shielding ultraviolet rays. As the metal, any of conventionally known materials can be used. For example, gold, silver, copper, aluminum, Although chromium, iron, nickel and the like can be exemplified, aluminum can be preferably used.

The oxygen barrier property of the metal vapor-deposited film (14) having the metal vapor-deposited film (142) is such that the oxygen permeability according to JIS K7126 is 1.0 cc / m ² · day · atm (temperature 22 ° C., humidity 65% RH). It is desirable that:

  Further, as the ultraviolet shielding property as the metal vapor-deposited film (14), it is desirable that the light transmittance by SZ- # 80 manufactured by Nippon Denshoku Industries Co., Ltd. is 0.1% or less.

  The thickness of the above-described metal vapor-deposited film (142) 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 deposition film (142), any conventionally known thin film formation method may be used. For example, a physical vapor deposition method such as a vacuum deposition method, a sputtering method, or an ion plating method And the like.

  Prior to the formation of the metal vapor-deposited film (142), there is no problem even if the surface of the vapor-deposited film substrate (141) is subjected to a surface treatment such as a corona treatment, a plasma treatment, or an ion bombardment treatment.

  In the case where the metal-deposited film (14) as described above is used as an oxygen barrier layer, in a post-processing step for the metal-deposited film, a metal-deposited surface is provided in the transport path of the metal-deposited film (14). When a roll or coating plate or a rolled-up metal vapor deposition film (14) is unwound, the metal vapor deposition film (142) is rubbed against the rear surface of the metal vapor deposition film substrate (141). In some cases, partial omission occurred, and the oxygen barrier property originally possessed by the metallized film (14) was impaired.

  In order to solve such a problem, the present inventors have proposed a layer configuration capable of compensating for the reduced oxygen barrier property even in the case where the above-described metal oxide film (142) is partially missing. As a result, a method for forming a laminate that can be used as an outer bag for a chemical solution without using an additional reinforcing layer has been found.

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

  Such an anchor coating agent layer (13) is mainly composed of, for example, a 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-based resins, oxazoline group-containing resins, modified styrene resins, modified silicon 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 a curing agent, a catalyst, a stabilizer, and an initiator can be added to the anchor coat agent layer (13), depending on the resin used.

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

  The inorganic layered mineral is an inorganic compound in which ultra-thin unit crystal layers overlap to form one layered particle. As the inorganic layered mineral, those which swell and cleave in water are preferable, and among these, Particularly, a clay compound having a property of swelling in water is preferably used, and this clay compound may be a natural compound or a synthetic compound.

  Representative examples of the inorganic layered mineral include hydrated silicates such as phyllosilicate minerals, for example, kaolinite-serpentine group clays such as halloysite, kaolinite, endrite, decite, nacrite, antigolite, 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, tetrasilicic Examples include mica or mica group clay minerals such as mica and teniolite.

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

The thickness of the anchor coat agent layer (13) provided with oxygen barrier properties by the addition of the inorganic layered mineral or the like as described above is about 3.0 to 5.0 g / m ² as a coated amount after drying. It 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 metallized film, and if it exceeds 5.0 g / m ^2. As compared with the oxygen barrier effect, the coating amount becomes excessive and the cost is disadvantageous.

  In order to improve the coatability and adhesiveness of the anchor coat agent layer (13), a corona treatment or the like may be applied to the surface of the metal vapor-deposited film (14) prior to the formation of the anchor coat agent layer.

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

  FIG. 3 is a cross-sectional view illustrating a configuration example of the sealant film (15) having an oxygen barrier property.

  As the sealant film (15), any film can be used as long as it can be heat-sealed and has an oxygen barrier property. As shown in FIG. 3, both surfaces of the oxygen barrier resin layer (151) can be used. A co-extruded film having a sandwich-like laminated structure sandwiching the sides between sealant material layers (152) can be suitably used.

  As the oxygen barrier resin layer (151), any resin having a conventionally known oxygen barrier property can be used. For example, a polyamide resin such as 6-nylon or polymethaxylylene adipamide (MXD6) or the like can be used. And ethylene-vinyl alcohol copolymer (EVOH).

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

  In addition, the sealant material layer (152) can use a polyolefin resin, and specifically, a low density polyethylene resin (LDPE), a linear low density polyethylene resin (LLDPE), and a 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 As examples, coalesced (EAA), ethylene-vinyl acetate copolymer (EVA), ionomer resins and the like can be mentioned.

  Among them, a linear low-density polyethylene resin (LLDPE) can be suitably 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) or less, and It is desirable that the seal strength at the time of heat fusion 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 metal-deposited film (142) is partially missing in the metal-deposited film (14), and the oxygen barrier property of the metal-deposited film (14) is impaired. In this case, it is possible to supplement the oxygen barrier properties of the laminate (1).

  Further, even when used as an outer bag for a container having a weight such as a primary container filled with a chemical solution, the outer bag is provided with a sufficient sealing strength so that the outer bag is not easily broken and a safe outer bag is provided. It becomes possible.

  As described above, each layer of the base film (11), the metal-deposited film (14) including the anchor coat agent layer (13), and the sealant film (15) is sandwiched by the sandwich lamination method via the extruded resin layer (12). It is laminated.

  For the extruded resin layer (12), a commercially available extruded resin can be used, and low-density polyethylene resin (LDPE), medium-density polyethylene resin (MDPE), and 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-acrylic acid ester copolymer (EEA), or the like can be used.

  The thickness of the extruded resin layer is desirably about 10 to 30 μm. As described above, by using the sandwich lamination method using the extruded resin layer, it is possible to provide a thick resin layer as compared with the dry lamination method in which the adhesive resin is coated and laminated.

  Therefore, even if a reinforcing layer or the like required when the dry lamination method is used is not provided, even if the primary packaging bag filled with the chemical liquid is enclosed, the outer packaging for the chemical liquid which does not generate pinholes even when subjected to an impact in a transportation operation or the like during transportation work. The laminate can provide a bag.

  The embodiments described below are merely examples, and the present invention is not necessarily limited to the embodiments described below.

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

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

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

(Base film)
Stretched propylene film (OPP) ... FOS 50 μm manufactured by Futamura Chemical Co., Ltd.
(Metal evaporated film)
PET film with aluminum deposited… Oike Pack Material Co., Ltd.
JC-V8 12 μm
(Sealant film)
Co-extruded film (LLDPE / EVOH / LLDPE)-Tamapoli Corporation
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 Nippon Polyethylene Co., Ltd.
LC600A 20 μm
(Anchor coat agent layer)
Two-component curing type polyester polyol: DIC Corporation
PASLIM VM001 4.8 μm

<Comparative Example 1>
Laminate sample 2 was produced in the same manner as in Example 1 except that an LLDPE film having no oxygen barrier property (L-smart (registered trademark) manufactured by Mitsui Chemicals Tosello Co., Ltd.) was used as the sealant film.

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

<Comparative Example 3>
As the anchor coat agent layer, a urethane-based material having no oxygen barrier property (A3210 manufactured by Mitsui Chemicals, Inc.) is used, and as a sealant film, LLDPE having no oxygen barrier property (EL SMART (registered trademark) Mitsui Chemicals East Sero Corporation) A laminate sample 4 was produced in the same manner as in Example 1 except that the above-mentioned) was used.

  As described above, two kinds of evaluations of Experiment 1 and Experiment 2 shown below were performed on each of the manufactured laminate samples.

<Experiment 1>
For each of the laminate samples 1-4 prepared according to Example 1, Comparative Example 1, Comparative Example 2, and Comparative Example 3 and the metal-deposited film before processing used in each sample, the temperature was 22 ° C. and the humidity was 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 supplementing the deterioration of the oxygen barrier property due to the processing step at the time of manufacturing the laminate by using an anchor coat agent layer and a sealant film having oxygen barrier properties. It was 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, only the sealant film was used instead of only the anchor coat agent layer having oxygen barrier properties. It was found that the case having the oxygen barrier property compensated for the deterioration of the oxygen barrier property.

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

According to the results of Comparative Example 1 and Comparative Example 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 a certain degree of oxygen barrier property can be maintained, in a high-temperature and high-humidity environment at a temperature of 40 ° C. and a humidity of 70% RH, the oxygen permeability should be around 1.0 cc / m ² · day · atm or more. It turns out that it shows.

In the case of an outer bag for putting a primary container filled with a drug solution for medical use, a value of 1.0 cc / m ² · day · atm or less is required, 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 the configuration of the laminate shown in Example 1 could secure a stable oxygen barrier property even in a high-temperature and high-humidity environment.

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

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

Claims (4)

From the outside, a substrate film, a metallized film, a laminate formed by laminating a sealant film at least in this order via an extruded resin layer,
An anchor coat agent layer is provided on the metal deposition surface side of the metal deposition film,
A laminate, wherein the anchor coat agent layer and the sealant film have oxygen barrier properties. The oxygen permeability of the sealant film is 0.8 cc / m ² · day · atm or less, and the seal strength when the sealant films are heat-sealed to each other is 50 N / 15 mm or more. The laminate according to claim 1.   3. The laminate according to claim 1, wherein the sealant film is a co-extruded film in which a linear low-density polyethylene resin is laminated on both sides of an ethylene-vinyl alcohol copolymer. 4.   The laminate according to any one of claims 1 to 3, wherein the anchor coat agent layer contains an inorganic layered mineral.

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