JP2019217734A - Laminate - Google Patents

Abstract

To produce a laminate capable of providing an outer packaging bag for a chemical solution inexpensively without using a special reinforcement layer while using an aluminum vapor deposition film as an oxygen barrier layer and an ultraviolet light shielding layer.SOLUTION: A laminate is obtained by laminating a substrate film, an aluminum vapor deposition film and a sealant film at least in this order from an outside. The aluminum vapor deposition film has oxygen permeation of 1.0 cc/mday atm or less, is drawn, and has an orientation angle of a molecular chain measured by a phase-difference measurement method of from 55° to 90° or from -55° to -90° with regard to an MD direction. An anchor coat agent layer is laminated at least on a vapor deposition surface of the aluminum vapor deposition film.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a laminated body for a packaging bag, in which a pinhole is unlikely to be generated when packing and transporting an object having a thickness and weight, using a laminated packaging material having an oxygen barrier property and an ultraviolet shielding property. 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 danger of being damaged by impact, and are bulky and inconvenient for transportation and storage. 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 may be filled in a flexible plastic primary container as disclosed in Patent Document 1, for example, from the viewpoints 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 significantly deteriorated by oxygen, and vitamins are easily deteriorated by near ultraviolet rays in many cases.

  On the other hand, since these chemicals may be injected directly into the body, a bag-shaped container that comes into direct contact with these chemicals should be used in such a way that the elution of components from the container itself does not 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 shielding property as described above include, for example, aluminum foil. When the aluminum foil is laminated with a plastic film, the barrier effect is excellent, but the plastic bag is excellent. It is inevitable that the bag is harder than the type, and there are difficulties in handling depending on the use, and the price is expensive.

  On the other hand, there is a concept of using an aluminum vapor-deposited film, but in a general aluminum vapor-deposited film, the aluminum vapor-deposited film may be easily damaged due to contact with a roll or the like in a processing step, so that a relatively scratch is 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 disclosed 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 an aluminum vapor-deposited film are dry-laminated in advance, A method of so-called extrusion lamination in which the outermost layer and the innermost layer are laminated via an extruded resin to the previously dry-laminated film after the layer is protected has also been proposed.

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

  In view of such circumstances, the present invention is to prepare a laminate capable of providing an outer bag for a chemical solution at low cost without using a special reinforcing layer while using an aluminum vapor-deposited film as an oxygen barrier layer and an ultraviolet shielding layer. It is assumed that.

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, an aluminum-deposited film, and a sealant film are laminated at least in this order, and the aluminum-deposited film has an oxygen permeability of 1.0 cc / m. ² · day · atm or less, and stretched, and the orientation angle of the molecular chain measured by the phase difference measurement method is 55 ° to 90 ° or −55 ° to −90 ° with respect to the MD direction. A laminate comprising an aluminum coating film and an anchor coating agent layer laminated on at least a deposition surface of the aluminum deposition film.

  The invention according to claim 2 is the laminate according to claim 1, wherein the anchor coat agent layer is laminated on both surfaces of an aluminum-deposited film.

  The invention according to claim 3 is the laminate according to any one of claims 1 and 2, wherein the anchor coat agent layer is a urethane-based adhesive.

  According to the present invention, it is possible to provide an extruded laminate that can be used as an outer bag for a chemical solution without using a special reinforcing layer while using an aluminum-deposited film as a barrier layer and an ultraviolet shielding layer.

It is sectional drawing which shows the structural example of the laminated body of this invention. It is sectional drawing which shows the structural example of the aluminum vapor deposition film of this invention. It is explanatory drawing which shows the definition about the orientation angle of the aluminum vapor deposition film of this invention. 4 is a graph showing the relationship between the orientation angle and the oxygen barrier property of the aluminum-deposited film of the present invention.

  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 showing a configuration example of the laminate of the present invention.

  FIG. 1 shows that a base film (11), an aluminum vapor-deposited film (14) provided with an anchor coat agent layer (13) on both sides, and a sealant layer (15) are laminated via an extruded resin layer (12). A configuration example is shown.

  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, Nylon, polyamide films such as MXD6 (polymethaxylylene adipamide), polycarbonate films, polyacrylonitrile films, polyimide films, polyvinyl alcohol films, polyvinylidene chloride films, etc., but those having mechanical strength and dimensional stability If so, there is no particular limitation. In particular, a biaxially stretched film or the like is preferable, and the thickness of the base film is preferably in the range of 10 to 50 μm in consideration of workability.

  Further, the base film (11) may be provided with a printing layer or the like as necessary, if necessary. As the print layer, an ink or the like obtained by optionally adding various pigments, extender pigments and plasticizers, desiccants, stabilizers, and the like to a conventionally known binder resin such as a urethane type, an acrylic type, a nitrocellulose type, and a rubber type is used. Can be configured.

  As a printing method, for example, conventionally known methods such as offset printing, gravure printing, flexographic printing, silk screen printing, and 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 aluminum vapor-deposited film (14) is provided with an aluminum vapor-deposited film (142) on a vapor-deposited film substrate (141). The agent layer (13) is laminated. As shown in FIG. 2, the anchor coat agent layer (13) may be provided on both sides of the aluminum vapor-deposited film (14).

  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-polyvinyl 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 and ease of handling.

  Here, in the vapor-deposited film substrate (141), the orientation angle of the molecular chain measured by the phase difference measurement method is from 55 ° to 90 ° or from −55 ° to −MD with respect to the MD direction (machine direction: flow direction). 90 °.

  Here, as shown in the figure, the orientation angle is 0 ° in the MD direction, (+) when the molecular chains are aligned to the left and (−) when the molecular chains are aligned to the right. Define. In addition, TD (Transvers Direction) in the figure has shown the width direction of the aluminum vapor deposition film (14).

The orientation angle of a molecular chain can be determined by using a method such as a phase difference measurement method using visible light or a molecular orientation measurement method using a microwave, but in the case of a molecular orientation measurement method using a microwave, The variation of the specific value by the measurer increases.

  On the other hand, in the phase difference measurement method, the measurement can be performed stably regardless of the operator, and there is little variation in measured values. Moreover, since the orientation angle can be accurately measured, it is desirable to use a phase difference measurement method in the measurement of the orientation angle of the molecular chain.

  The present inventors have studied the cause of the decrease in the oxygen barrier property of the aluminum vapor-deposited film (14), that is, the cause of the increase in oxygen permeability. In the process of transporting the aluminum vapor-deposited film (14), the aluminum vapor-deposited surface forms a roll or a coating plate in the apparatus, or the rear surface of the rolled-up aluminum vapor-deposited film (14) during unwinding. It has been found that abrasion with the vapor-deposited film substrate (141) or the like causes partial loss of the aluminum vapor-deposited film (142).

  Further, the friction between the aluminum vapor-deposited film (142) and a roll or a coating plate in the apparatus, the vapor-deposited film substrate (141), etc. causes slight deformation (slack, slack, wrinkle, etc.) of the aluminum vapor-deposited film (14). ) Was found to be caused by fluttering and misalignment of the aluminum vapor-deposited film (14) during transportation.

  Further, such slight bending of the aluminum vapor-deposited film (14) can be reduced by setting the molecular chain orientation angle of the vapor-deposited film substrate (141) within a predetermined range. Was found.

  That is, the biaxially stretched film used for the vapor-deposited film substrate (141) is usually biaxially stretched and then maintained at an appropriate heat-setting temperature, so that the molecular chains are arranged in a certain direction. The orientation angle with respect to the MD direction is determined by the orientation angle of the molecular chain.

  By setting the molecular chain orientation angle with respect to the MD direction from 55 ° to 90 ° or from −55 ° to −90 °, it is possible to reduce the bending of the aluminum vapor-deposited film (14), and as a result, the aluminum vapor-deposited film ( 142) Partial loss such as abrasion can be suppressed.

  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 aluminum deposition film (142) is provided for the purpose of providing oxygen barrier properties and blocking ultraviolet rays.

As the oxygen barrier property of the aluminum vapor-deposited film (14) having the aluminum 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). Bottom) It is desirable that:

This is because, in general, an outer bag serving as an outer bag for a primary container filled with a drug solution such as an amino acid solution, a sugar, or an electrolyte solution is required to have an oxygen permeability of 1.0 cc / m ² · day · atm or less. It is because it is.

  Further, as for the ultraviolet shielding property as the aluminum 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 aluminum 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 aluminum vapor-deposited film (142), any conventionally known thin-film forming method may be used, and for example, a physical vapor deposition method such as a vacuum vapor deposition method, a sputtering method, and an ion plating method. And the like.

  Prior to the formation of the aluminum 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.

  An anchor coat agent layer (13) is provided on at least the vapor deposition surface side of the aluminum vapor-deposited film (14) obtained as described above, that is, on the aluminum vapor-deposited film (142).

  The anchor coat agent layer (13) is, 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, imine resin, It is selected from oxazoline group-containing resins, modified styrene resins, modified silicon resins, alkyl titanates, and the like, and these can be used alone or in combination of two or more.

  Further, various additives such as a curing agent, a catalyst, a stabilizer, and an initiator may be added to the anchor coat agent layer (13) according to the resin used.

  In particular, a urethane-based adhesive such as a two-component curable urethane-based resin can be suitably used.

  The anchor coating agent layer (13) can usually have a thickness of about 5 nm to 5 μm. The anchor coating agent layer (13) having such a thickness can be formed on the surface of the aluminum vapor-deposited film (14) with a uniform thickness in which internal stress is suppressed. A more preferred thickness of the anchor coating agent layer (13) is 10 nm to 1 μm.

  In order to improve the coating property and adhesiveness of the anchor coating agent layer (13), the surface of the aluminum vapor-deposited film (14) may be subjected to corona treatment or the like prior to the 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 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 suitably used.

  For the sealant layer (15), a polyolefin-based resin can be used, and specifically, a low-density polyethylene resin (LDPE), a linear low-density polyethylene resin (LLDPE), a medium-density polyethylene resin (MDPE), Polyethylene resin (HDPE), polypropylene resin (PP), ethylene-propylene copolymer (EP), ethylene-α olefin copolymer, ethylene-methacrylic acid copolymer (EMAA), ethylene-acrylic acid copolymer (EAA) ), Ethylene-vinyl acetate copolymer (EVA), ionomer resins, and the like.

  Such a sealant layer (15) may be a single layer or a multilayer structure having two or more layers without any problem.

  As described above, the base film (11), the aluminum vapor-deposited film (14) including the anchor coat agent layer (13), and the sealant layer (15) are laminated via the extruded resin layer (12). .

  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) and 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 extrusion lamination method using the extruded resin layer, it becomes possible to provide a thicker 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, an outer layer for a chemical solution that does not generate pinholes even when subjected to an impact during transportation work after enclosing the primary packaging bag filled with the chemical solution. The laminate can provide a bag.

  The embodiments described below show one example, and the present invention is not necessarily limited to the following.

<Example 1>
Laminate sample 1 was prepared by laminating an aluminum vapor-deposited film and a sealant layer in this order by extrusion lamination using polypropylene as the surface layer base film.

  At that time, an aluminum vapor-deposited film having a molecular chain orientation angle of 55 ° with respect to the MD direction was used, and the following anchor coat agent layer was provided on the aluminum vapor-deposited surface.

(Base film)
Stretched propylene film (OPP) ... FOS 50 μm manufactured by Futamura Chemical Co., Ltd.
(Aluminum deposited film)
PET film with aluminum deposition… Oike Pack Material Co., Ltd.
JC-V8 12 μm
(Sealant layer)
Linear low-density polyethylene film (LLDPE)… manufactured by Mitsui Chemicals East Cello Co., Ltd.
L Smart C-1 40μm
(Extruded resin layer)
Low density polyethylene: manufactured by Nippon Polyethylene Co., Ltd.
LC600A 20 μm
(Anchor coat agent layer)
Two-part curable urethane resin

<Example 2>
A laminate sample 2 was produced in the same manner as in Example 1, except that an aluminum-deposited film having a molecular chain orientation angle of 67 ° with respect to the MD direction was used.

<Comparative Example 1>
A laminate sample 3 was produced in the same manner as in Example 1, except that an aluminum-deposited film having a molecular chain orientation angle of 48 ° with respect to the MD direction was used.

<Comparative Example 2>
A laminate sample 4 was produced in the same manner as in Example 1, except that an aluminum-deposited film having a molecular chain orientation angle of 52 ° with respect to the MD direction was used.

  Oxygen permeability according to JIS K7126 under the conditions of a temperature of 22 ° C. and a humidity of 65% RH for each of the aluminum vapor-deposited films used in Example 1, Example 2, Comparative Example 1, and Comparative Example 2 and the laminate samples prepared respectively. Was measured to confirm the change in oxygen permeability before and after processing the laminate.

  Table 1 shows the measurement results.

From the results of Example 1 and Example 2, when the orientation angle is 55 ° or more, the amount of change in oxygen permeability before and after processing the laminate is less than 0.2 cc / m ² · day · atm. On the other hand, from the results of Comparative Example 1 and Comparative Example 2, it was found that when the orientation angle was less than 55 °, the amount of change in oxygen permeability was 0.2 cc / m ² · day · atm or more. Was.

  That is, when an aluminum vapor deposition film having an orientation angle of 55 ° or more is used, fluttering (slack, twisting, wrinkling, etc.) of the aluminum vapor deposition film during transport, which is caused by fluttering or displacement, is reduced. Therefore, it can be considered that this is because the occurrence of partial chipping due to the rubbing of the aluminum vapor-deposited film is suppressed.

  Therefore, it is considered that the difference in oxygen permeability between before and after the processing of the laminate is small, and a sufficient oxygen barrier effect is exhibited.

<Additional experiment>
In the same manner as in the above Examples and Comparative Examples, for each of the cases where the orientation angle is 55 ° or more and the case where the orientation angle is less than 55 °, the number of prototype samples is added. That is, FIG. 4 shows the results of measuring the oxygen permeability of the laminated product (laminate product).

As shown in FIG. 4, when the orientation angle is 55 ° or more, the variation in oxygen permeability is stable within a range of about 0.4 cc / m ² · day · atm. Is less than 55 °, the variation in oxygen permeability is large, and in consideration of the variation in oxygen permeability of the aluminum-deposited film itself before processing the laminate, 1 is required for the outer bag for the primary container filled with the chemical solution. It can be considered to indicate a possibility of exceeding the oxygen permeability of 0.0 cc / m ² · day · atm or less.

  From the above results, by using the laminate of the present invention, the primary container filled with the chemical solution has sufficient characteristics as an outer bag, and a reinforcing layer for satisfying various required characteristics is not particularly required. An inexpensive laminate for an outer bag can be provided.

DESCRIPTION OF SYMBOLS 10 ... Laminated body 11 ... Base film 12 ... Extruded resin layer 13 ... Anchor coating agent layer 14 ... Aluminum vapor deposition film 15 ... Sealant layer

Claims (3)

From the outside, a base body film, an aluminum vapor-deposited film, a laminate obtained by laminating a sealant film at least in this order,
The aluminum vapor-deposited film has an oxygen permeability of 1.0 cc / m ² · day · atm or less,
It is stretched, and the orientation angle of the molecular chain measured by retardation measurement is from 55 ° to 90 ° or −55 ° to −90 ° with respect to the MD direction,
A laminate, wherein an anchor coat agent layer is laminated on at least a vapor deposition surface of the aluminum vapor-deposited film.   2. The laminate according to claim 1, wherein the anchor coat agent layer is laminated on both sides of the aluminum vapor-deposited film. 3.   The laminate according to claim 1, wherein the anchor coat agent layer is a urethane-based adhesive.