JP2002028999A - Gas barrier film laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plastic film laminate for infusion solution showing enhanced oxygen and moisture gas barrier and little elution during storage which is usable for an infusion solution container regulated by the testing method of a plastic-made medicine container according to Japan Pharmacopeia by making a gas barrier plastic film layer thinner. SOLUTION: A gas barrier film laminate is obtained by laminating an inorganic layer 2, a coating layer 3, an adhesive layer 4 and a protective film 5 in this order on at least on one surface of a plastic film 1 wherein the laminate shows a light transmission of not less than 55%, a hue b value of not more than 5, an oxygen transmission of not more than 1 cc/m2.day.atm measured in a dry atmosphere at 40 deg.C and a moisture transmission of not more than 1 cc/m2.day.atm and further the gas barrier plastic film has thickness of not more than 15 μm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film laminate used as a container material for storing and storing infusions such as drug solutions such as antibiotics, Ringer's carbonate solution, vitamin solution and amino acid solution.

[0002]

2. Description of the Related Art Conventionally, glass containers have been used as containers for chemical liquids, particularly for infusion solutions. However, there is a need in the market for reducing the weight and size of containers and improving the impact resistance of containers. In addition, plastic materials have been used as containers. Compared with glass containers, plastic containers have a higher gas permeability such as oxygen and a higher water vapor permeability, which lowers the quality of infusion solutions. there were. In recent years, thin films of silica (SiOx) and alumina (AlOx) have been formed using plastic vapor deposition (CVD) techniques to reduce the permeability of plastics such as oxygen gas and water vapor. Various films formed thereon have been proposed (JP-A-5-8318, etc.). However, such a film cannot be used for infusion because many organic substances are eluted from the PET film. On the other hand, a so-called polyolefin film such as polyethylene or polypropylene does not have the above problem, and can be used as a film for infusion. However, even if aluminum is vapor-deposited on a normal polypropylene film, the gas barrier property against oxygen or the like is not sufficient (Japanese Patent Laid-Open No. 3-115329). In order to improve the gas barrier properties of the polypropylene film, it has been attempted to coat polyvinylidene chloride on the polypropylene film (Japanese Patent Application Laid-Open No. 63-257630). However, when incinerating a plastic containing polyvinylidene chloride, It is not preferred because dioxin may be generated.

[0003]

SUMMARY OF THE INVENTION The present invention has solved the above-mentioned problems, that is, it has improved oxygen and water vapor gas barrier properties,
The present invention also relates to a laminate of a plastic film that has a small amount of eluted substances during storage. More specifically, the present invention provides a plastic film for infusion which can be used as an infusion container specified by the Japanese Pharmacopoeia Plastic Container Test Method by thinning the plastic film of the gas barrier layer.

[0004]

The present invention provides (1) the following physical property values obtained by sequentially laminating an inorganic layer / coating layer / adhesive layer / protective film on at least one surface of a plastic film as a gas barrier layer. A gas barrier film laminate comprising a laminate and a plastic film having a thickness of 15 μm or less, a light transmittance of 55% or more, a hue b value of 5 or less, and an oxygen gas permeability 1 measured at 40 ° C. in a dry atmosphere 1.
cc / m 2 · day · atm or less Water vapor transmission rate 1 g / m 2 · day · atm or less (2) The plastic film is characterized by using at least one selected from polyester, polyamide and ethylene-vinyl alcohol copolymer. The above (1)
(3) The gas barrier film laminate according to (1) or (2), wherein the inorganic layer is a silicon oxide-based thin film, and (4) the silicon oxide-based thin film is a nitrogen element. The gas barrier film laminate according to the above (3), which is a silicon oxynitride thin film containing: (5) the composition of the silicon oxynitride thin film is 4 to 64 atom% of oxygen and 3 to 5 nitrogen.
The gas barrier film laminate according to (4), wherein the gas barrier film laminate is 6 atomic% and the sum of the composition of oxygen and nitrogen is 75 atomic% or less. (1) to (1) to (1) to (2), which are composed of one or more selected from zinc oxide, aluminum oxide, titanium oxide and indium tin oxide (ITO).
(5) The gas barrier film laminate according to any of (5),
(7) The gas barrier film laminate according to any one of (1) to (6), wherein the adhesive resin is a polyolefin modified with an unsaturated carboxylic acid or a derivative thereof, (8) The gas barrier film laminate according to (7), wherein the modified polyolefin is an ethylene homopolymer or an ethylene-α-olefin random copolymer containing 10 mol% or less of another α-olefin, 9) The gas barrier film laminate according to the above (7), wherein the modified polyolefin is a propylene homopolymer or a propylene-α-olefin random copolymer containing 10 mol% or less of other α-olefin. , (10) the protective film is a polyethylene film, an ethylene-based polymer film and a propylene-based polymer film The gas barrier film laminate according to any one of the above (1) to (9), wherein the protective film is a polyethylene film kneaded with any one of the following modified polyolefins, and an ethylene polymer film. And the propylene-based polymer film, wherein the gas barrier film laminate according to the above (10), a polyolefin modified with an unsaturated carboxylic acid or a derivative thereof, an ethylene homopolymer or 10 mol% or less. Α-
Olefin-containing ethylene-α-olefin random copolymer Propylene homopolymer or 10 mol% or less of other α
-A olefin-containing propylene-α-olefin random copolymer (12) The gas barrier film laminate according to any one of the above (1) to (11), which is for a chemical container, and (13) the gas barrier film, which is for an infusion container. (1) The gas barrier film laminate according to any one of (1) to (11).

[0005]

FIG. 1 shows an example of a sectional view of a gas barrier film laminate of the present invention. An inorganic layer 2 such as silicon oxynitride, a coating layer 3 for improving the adhesion between the inorganic layer and the adhesive layer, an adhesive layer 4, and a protective film 5 such as a polyolefin film are sequentially laminated on the plastic film 1 serving as a gas barrier layer. It was done. The laminate of the present invention has a light transmittance of 55% or more, preferably 70% or more, a hue b value of 5 or less, preferably 3 or less, and an oxygen gas transmittance of 1 measured at 40 ° C. in a dry atmosphere.
cc / m 2 · day · atm or less, preferably 0.5 c
c / m 2 · day · atm or less, more preferably 0.2
cc / m 2 · day · atm or less, water vapor permeability 1 g / m 2 · day · atm or less,
Is a laminate having physical properties of:

[0006] The gas barrier film laminate of the present invention must have at least a gas barrier layer and a protective layer, and is provided with a coating layer and an adhesive layer to adhere these layers. In the present invention, the plastic film used as the gas barrier layer is made of polyester, especially polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyamide, especially nylon (N
Y), ethylene-vinyl alcohol copolymers such as Eval (EVOH) are preferably used. These films may be stretched films or unstretched films. Further, two different kinds of films may be used in a laminated state. The thickness of the film is 15
It is a feature of the present invention that it is not more than μm. More preferably, it is 12.5 μm or less. When such a thin film is used, when a liquid such as an infusion solution is packaged, the organic substance is hardly eluted into the infusion solution, which is preferable as a medicine packaging container for the infusion solution or the like.

As the inorganic layer formed on the plastic film, a silicon oxide-based thin film, particularly a silicon oxynitride thin film, is preferably used among transparent inorganic materials. Generally, a silicon oxide thin film and an alumina thin film are known as transparent vapor-deposited films. However, the present inventors have found that a silicon oxynitride thin film is excellent in gas barrier properties. As a method for forming the inorganic layer, techniques such as vacuum deposition, sputtering, and chemical vapor deposition (CVD) are suitably used. In order to sufficiently exhibit gas barrier performance, when the inorganic layer has the same thickness, it is more effective to form the inorganic layer on both sides of the plastic film with a half thickness than on one side.

In the case of a silicon oxynitride thin film, oxygen 4-6
Amorphous silicon oxynitride having 4 atomic%, 3 to 56 atomic% of nitrogen, and a sum of oxygen and nitrogen of 75 atomic% or less is preferable in terms of the barrier property and the transparency. The composition of silicon oxynitride can be analyzed by a technique such as X-ray photoelectron spectroscopy or Auger electron spectroscopy.

The thickness of the inorganic layer is not particularly limited, either.
If the thickness is too large, the thin film is easily cracked. If the thickness is too small, the gas barrier effect is small.
m, preferably 10 to 50 nm. In addition, if necessary, just before forming the inorganic layer, the surface of the plastic film may be treated to remove dirt and deposits on the surface.

[0010] The coating layer in the present invention is for good adhesion between the adhesive resin and the plastic film as the gas barrier layer. When a silicon oxide-based thin film is formed on the gas barrier layer, the adhesive resin and the silicon oxide-based thin film are used. Thin film,
Those showing good adhesion to both are preferred. In addition, since it is necessary to suppress the elution of organic substances to be used as an infusion container, zinc oxide, aluminum oxide, titanium oxide,
Inorganic substances such as indium tin oxide (ITO) are preferred. One or more of these inorganic substances may be used.

The coating layer is formed on the inorganic layer such as a silicon oxynitride thin film on a polyolefin film, which is a gas barrier layer, by a technique such as vacuum deposition, sputtering, or CVD. The thickness of the coating layer is
Since a certain thickness is required for uniform coating, the thickness is preferably 1 to 100 nm, more preferably 2 to 20 nm.

In the present invention, an adhesive resin is usually used for the adhesive layer, and a polyolefin modified with an unsaturated carboxylic acid or a derivative thereof is preferable. The polyolefin referred to herein is an ethylene homopolymer, an ethylene-α-olefin random copolymer containing ethylene and 10 mol% or less of other α-olefin, or a propylene homopolymer or 10 mol% or less of propylene. Propylene-α-olefin random copolymer containing other α-olefin is preferred.

The unsaturated carboxylic acids used for the modification include maleic acid, acrylic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, endocis-bicyclo [2,2,1] heptoate. -5-ene 2,3-dicarboxylic acid (trade name: nadic acid) and the like are preferable, and derivatives thereof include acid halides, amides, imides, anhydrides, esters, and the like. Specifically, maleenyl chloride, maleimide , Maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate and the like. Of these, unsaturated carboxylic acids or anhydrides thereof are preferred, and maleic acid, nadic acid or anhydrides thereof are particularly preferred. The thickness of the adhesive layer is not particularly limited, but is preferably thinner, preferably 0.5 to 100 μm, and more preferably 1 to 30 μm.

The protective film is a layer for protecting the barrier layer, and is preferably a polyolefin film. Polyolefin film as a protective layer is rigid, transparent,
In terms of heat sealing properties, polyethylene films, ethylene-based polymer films, and propylene-based polymer films are preferred, and linear low-density polyethylene, low-density polyethylene, medium-density polyethylene, propylene random copolymer, and propylene block copolymer It is more preferred to use The thickness of these protective films is not particularly limited, but is 5 to 500 μm, preferably 10 to 200 μm.

The above adhesive layer is not used as an independent layer, but may be a protective film into which an adhesive layer component is kneaded.

The laminate of the present invention is a gas barrier film laminate in which a plastic film / inorganic layer / coating layer / adhesive layer / protective film is laminated in this order. (Inorganic layer / plastic film / inorganic layer) may be laminated via an adhesive layer, and then a protective film may be laminated.

[0017]

EXAMPLE A method for producing the gas barrier film laminate shown in FIG. 1 will be described below with reference to examples. Note that the present invention is not limited to this.

Example 1 PET having a thickness of 12.5 μm
A silicon oxynitride thin film 2 was formed on the film 1 by sputtering using a 13.56 MHz high frequency power supply.
The film was formed by reactive sputtering of oxygen and nitrogen using silicon having a purity of 99.99% as a target.
When the film was formed at a pressure of 0.2 Pa and a supply power of 120 W for 5 minutes, the film thickness was 30 nm, and the ratio of silicon: oxygen: nitrogen was 37:17:46. As a coating layer 3 on the silicon oxynitride thin film 2 by sputtering using indium tin oxide (ITO) as a target,
An ITO layer was formed to a thickness of 5 nm.

On this ITO layer, a maleic acid-modified resin, specifically, a linear polyethylene having a density of 0.920 was 52% by weight, a high-pressure low-density polyethylene resin having a density of 0.920 was 15% by weight, and a density of 0.20%. 965, 15% by weight of a linear polyethylene, 10% by weight of an ethylene-α-olefin copolymer having a density of 0.850, and 2.% of a maleic ester.
8% of a linear polyethylene having a density of 0.965 containing 2% by weight.
The resin modified in an extruder was subjected to extrusion lamination so as to have a thickness of 20 μm as an adhesive layer 4, and a 100 μm-thick polyethylene film obtained in advance by cast molding was bonded to the protective film 5. Thus, a gas barrier film laminate (J1) of the present invention was obtained.

Example 2 A gas barrier film was laminated in the same manner as in Example 1 except that a NY film having a thickness of 12.5 μm was used as a gas barrier film and titanium oxide (thickness: 5 nm) was used as a coating layer. Body (J
2) was created.

Example 3 The thickness used in Example 1 was 1
13.5 on both surfaces of 2.5 μm PET film
A silicon oxynitride thin film was formed by sputtering using a 6 MHz high frequency power supply. The film was formed in the same manner as in Example 1, and a silicon oxynitride film having a thickness of 30 nm was formed. An ITO layer having a thickness of 5 nm was formed on each silicon oxynitride thin film by sputtering using indium tin oxide (ITO) as a target as a coating layer. A 20 μm-thick adhesive layer was formed on these ITO layers in the same manner as in Example 1, and a 100 μm-thick polyethylene film obtained in advance by casting was bonded to each surface to form a protective film. A laminate (J3) was obtained.

Comparative Example 1 A gas barrier film laminate (H1) was prepared in the same manner as in Example 1 except that a 38 μm thick PET film was used as a gas barrier film and no coating layer was formed.

Comparative Example 2 An unstretched polypropylene film having a thickness of 300 μm (CP) was used as a gas barrier film.
P), and a gas barrier film laminate (H) was prepared in the same manner as in Example 1 except that no coating layer was formed.
2) was created.

Table 1 summarizes the results of evaluating the physical properties of the gas barrier film laminates shown in Examples and Comparative Examples. The evaluation method of the laminated body was implemented by the following method. Oxygen gas permeability was measured using a MOCON gas permeation measuring device.
The temperature was measured at 0 ° C. and 0% RH. . Water vapor transmission rate is MO
40 ° C., 90 ° C. using a gas transmission measurement device manufactured by CON
% RH. The light transmittance and the b value (the ratio of yellow and blue) were measured with a Hitachi spectrophotometer U-3400. Light transmittance was measured at a wavelength of 450 nm.

[0025]

[Table 1]

Further, the gas barrier film laminates of J1, 2, 3, H1, and J2 were subjected to steam sterilization at 115 ° C. for 40 minutes, and then the peel strength was measured. The peel strength measurement of the gas barrier film laminate is 1.5 cm in width and 10 cm in length.
And measured at a tensile speed of 50 mm / min. In all the laminates of J1, 2, 3, H1, and H2, peel strength of 600 gf or more was maintained even after steam sterilization.

(Test Example 1) An eluate test was carried out based on the test method for plastic containers for infusions of the Japanese Pharmacopoeia. J1,
Tests were performed on each of the gas barrier film laminates of 2, 3, H1, and 2 in an area of 600 cm2. These film laminates were finely chopped to a length of 5 cm and a width of 0.5 cm, washed in distilled water and dried at room temperature. This was put in a hard glass container having a content of about 300 mL, and after adding 200 mL of distilled water, the container was sealed, heated at 121 ° C. for 1 hour, and then cooled to room temperature. Thereafter, the cut gas barrier film laminate was removed to obtain an aqueous solution from which residues were eluted. The aqueous solution was concentrated, and the UV absorbance was measured. Further, the water content of the aqueous solution was evaporated, the residue was dried and the weight thereof was measured. The values for J1 were compared, and the results are shown in Table 2.

The laminated films other than H1 passed the extract test of the plastic container test for infusion specified in the Japanese Pharmacopoeia.

[0029]

[Table 2]

[0030]

EFFECTS OF THE INVENTION The gas barrier film laminate produced by the present invention is transparent, has excellent steam sterilization properties, gas barrier properties, and water vapor barrier properties, and elutes into an infusion even when packaging a liquid such as an infusion. It can be suitably used as a medicine packaging container for infusions and the like because of its small amount.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a gas barrier film laminate showing an example of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Fastic film which is a gas barrier layer 2 Inorganic material layer, such as silicon oxynitride 3 Coating layer 4 Adhesive layer 5 Protective film

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 3E086 AD01 BA04 BA13 BA15 BB02 BB05 CA28 4F100 AA01B AA12B AA19C AA20B AA21C AA25C AA33C AK01A AK03G AK04D AK06 AK07D AK07G AK24D AK24GAK AK24G AK24G AK24G AK24A DA01 EJ91D GB16 JA12B JD02 JM02B

Claims (13)

[Claims] 1. A laminate having the following physical properties in which an inorganic layer / coating layer / adhesive layer / protective film is sequentially laminated on at least one surface of a plastic film as a gas barrier layer, wherein the thickness of the plastic film is A gas barrier film laminate having a thickness of 15 μm or less. Light transmittance 55% or more Hue b value 5 or less Oxygen gas transmittance measured at 40 ° C in a dry atmosphere 1
cc / m 2 · day · atm or less Water vapor permeability 1 g / m 2 · day · atm or less 2. The plastic film is made of polyester,
The gas barrier film laminate according to claim 1, wherein at least one selected from polyamide and ethylene-vinyl alcohol copolymer is used. 3. The gas barrier film laminate according to claim 1, wherein the inorganic layer is a silicon oxide-based thin film. 4. The gas barrier film laminate according to claim 3, wherein the silicon oxide-based thin film is a silicon oxynitride thin film containing a nitrogen element. 5. An amorphous silicon oxynitride film in which the composition of a silicon oxynitride thin film is 4 to 64 atomic% of oxygen, 3 to 56 atomic% of nitrogen, and the sum of the composition of oxygen and nitrogen is 75 atomic% or less. The gas barrier film laminate according to claim 4, wherein: 6. A coating layer comprising zinc oxide, aluminum oxide, titanium oxide and indium tin oxide (IT).
The gas barrier film laminate according to any one of claims 1 to 5, comprising one or more members selected from O). 7. The gas barrier film laminate according to claim 1, wherein the adhesive resin is a polyolefin modified with an unsaturated carboxylic acid or a derivative thereof. 8. The gas barrier film laminate according to claim 7, wherein the modified polyolefin is an ethylene homopolymer or an ethylene-α-olefin random copolymer containing 10 mol% or less of another α-olefin. body. 9. The gas barrier film laminate according to claim 7, wherein the modified polyolefin is a propylene homopolymer or a propylene-α-olefin random copolymer containing 10 mol% or less of another α-olefin. body. 10. The protective film according to claim 1, wherein the protective film is any one of a polyethylene film, an ethylene-based polymer film, and a propylene-based polymer film.
10. The gas barrier film laminate according to item 9. 11. A protective film is a polyethylene film kneaded with any of the following modified polyolefins:
The gas barrier film laminate according to claim 10, which is any one of an ethylene-based polymer film and a propylene-based polymer film. Polyolefins modified with unsaturated carboxylic acids or derivatives thereof Ethylene homopolymer or 10 mol% or less of other α-
Olefin-containing ethylene-α-olefin random copolymer Propylene homopolymer or 10 mol% or less of other α
-Propylene-α-olefin random copolymer containing olefin 12. The gas barrier film laminate according to claim 1, which is for a chemical container. 13. The gas barrier film laminate according to claim 1, which is for an infusion container.