JP2001315276A - Polyolefin laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plastic film for fluid which can be used for a fluid container as prescribed by the test method for a plastic medicine container of the Japan Pharmacopeia by making up all of individual plastic film layers of a polyolefin film as a constitytent material of a plastic film laminate. SOLUTION: The polyolefin film laminate obtained by laminating a least a gas barrier layer formed of the polyolefin film and a protecting layer formed likewise of the polyolefin film, is a polyolefin laminate with a light rays permeability of 55% or higher, a hue (b) value of 5 or less, an oxygen gas permeability, as measured at 40 deg.c and under a dry atmosphere, of 50 cc/m2/day/atm or less and a water vapor permeability of 2 g/m2/day/atm or less.

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 (SiO _x ) and alumina (AlO _x ) have been formed using techniques such as vacuum evaporation, sputtering, and chemical vapor deposition (CVD) in order to reduce the gas permeability of plastics such as oxygen and water vapor. Various films formed on a plastic film such as PET have been proposed (JP-A-5-8318, etc.). However, if such a film is used for an infusion solution, there are many eluted substances from the PET film, and it cannot be used. In the Japanese Pharmacopoeia Plastics Container Test Method, polyester such as PET is not described as a material of an infusion container.

On the other hand, so-called polyolefins such as polyethylene and polypropylene do not have the above-mentioned problems, and can be used as films for infusion. However, even if aluminum is vapor-deposited on a normal polypropylene film, the gas barrier property against oxygen and the like is not sufficient (Japanese Patent Laid-Open No. 3-1)
No. 15329).

[0005] 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, plastics containing polyvinylidene chloride are incinerated. In doing so, it is not preferred because dioxin may be generated.

[0006]

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 does not elute during storage. More specifically, as a constituent material of a plastic film laminate, an infusion solution that can be used as an infusion container specified by the Japanese Pharmacopoeia Plastics Container Test Method by being composed of a polyolefin film for each layer of plastic film. A plastic film for use.

[0007]

The present invention relates to (1) a polyolefin film laminate obtained by laminating at least a gas barrier layer composed of a polyolefin film and a protective layer composed of a polyolefin film, the laminate having the following physical properties. The light transmittance is 55% or more. The hue b value is 5 or less. The oxygen gas transmittance measured at 40 ° C. in a dry atmosphere is 50 cc / m ² · day · atm or less. The water vapor transmittance is 2 g / m ² · day · atm or less (2) The polyolefin laminate according to (1), wherein a transparent silicon oxide-based thin film is formed on at least one surface of a polyolefin film serving as a gas barrier layer, and (3) the silicon oxide-based thin film contains a nitrogen element. The polyolefin laminate according to the above (2), which is silicon oxynitride; (4) the composition of the silicon oxynitride thin film is 4 to 64 atom% of oxygen, nitrogen 3 The polyolefin laminate according to the above (3), which is an amorphous silicon oxynitride having 56 atomic% and the sum of the composition of oxygen and nitrogen is 75 atomic% or less, and (5) the softening temperature of the polyolefin film which is a gas barrier layer. The laminate according to any one of (1) to (4), wherein (TMA) is 70 ° C. or higher, and (6) the polyolefin film serving as a gas barrier layer has a copolymer structure of cycloolefin and α-olefin. The polyolefin laminate according to any one of the above (1) to (5), (7) a cyclic olefin (cy
(6) the polyolefin laminate according to the above (6), wherein the copolymer of cloolefin) and the α-olefin is represented by the following formula (I):

[0008]

Embedded image

(8) A thin film of silicon oxynitride / a coating layer having good adhesion with an adhesive resin / an adhesive layer made of an adhesive resin /
The polyolefin laminate according to any one of the above (1) to (7), wherein a protective layer composed of a polyolefin film is sequentially formed, (9) the coating layer is zinc oxide, aluminum oxide, titanium oxide, and indium tin oxide. (I
(10) The polyolefin laminate according to the above (8), wherein the polyolefin laminate comprises one or more kinds selected from TO).
The polyolefin laminate according to the above (8) or (9), wherein the adhesive resin is a modified polyolefin which is an unsaturated carboxylic acid or a derivative thereof, (11) the modified polyolefin is ethylene homopolymerized or 10 mol% or less of other α- (10) The polyolefin laminate according to the above (10), which is an ethylene-α-olefin random copolymer containing an olefin, or (12) the modified polyolefin is propylene homopolymer or propylene containing not more than 10 mol% of another α-olefin. (13) The polyolefin laminate according to the above (1), which is an α-olefin random copolymer, (13) the polyolefin laminate according to the above (1), wherein the polyolefin film of the protective layer is a polyolefin film kneaded with an adhesive resin, 14) The above (1) which is for a chemical container
Polyolefin laminate according to any one of-(13),
(15) The polyolefin laminate according to any one of (1) to (13), which is for an infusion container.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The polyolefin laminate according to the present invention has at least a gas barrier layer and a protective layer, and these layers must all be polyolefin films. FIG. 1 shows an example of a cross-sectional view of the polyolefin film laminate of the present invention. A silicon oxide-based thin film 2, a coating layer 3 for increasing the adhesion between the silicon oxide-based thin film and the adhesive layer, an adhesive layer 4, and a polyolefin film 5 as a protective layer are sequentially laminated on a polyolefin film 1 as a gas barrier layer. It is. The polyolefin laminate of the present invention has the following physical properties. The light transmittance is 55% or more, preferably 70% or more, the hue b value is 5 or less, preferably 3 or less. The oxygen gas transmittance measured at 40 ° C. in a dry atmosphere is 50 cc / m ² · day · atm or less. , Preferably 10 cc / m ² · day · atm or less, more preferably 5 cc / m ² · day · atm or less, and water vapor permeability of 2 g / m ² · day · atm or less,
It is preferably at most 1 g / m ² · day · atm.

The polyolefin film used as the gas barrier layer in the present invention includes linear low-density polyethylene, low-density polyethylene, medium-density polyethylene, high-density polyethylene, propylene homopolymer, propylene random copolymer, propylene block copolymer and the like. Other
Examples thereof include copolymers of a cycloolefin and an α-olefin described in JP-A-8-142263. Among them, the softening temperature (TMA) of the film is 7
A polyolefin film having a temperature of 0 ° C. or higher is preferred, and a copolymer of a cycloolefin and an α-olefin, particularly a structure represented by the chemical formula (I) is preferred. These films may be stretched films or unstretched films.

[0012] The thickness of the polyolefin film as the gas barrier layer is not particularly limited, since the strength of the film is difficult to obtain if it is too thin, and the film lacks flexibility if it is too thick. ３００300 μm.

The polyolefin film as the gas barrier layer is formed by depositing a transparent inorganic thin film by vacuum evaporation, sputtering, or the like in order to enhance gas barrier properties and water vapor barrier properties.
It may be coated by a technique such as chemical vapor deposition (CVD).

Among the inorganic substances, a silicon oxide-based thin film, particularly a silicon oxynitride thin film, is preferable. 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 the above-mentioned barrier properties. In order to sufficiently exhibit gas barrier performance, it is more effective to form the silicon oxynitride thin film on both sides of the polyolefin film with a half thickness than on one side when the silicon oxynitride thin film has the same thickness.

Further, the silicon oxynitride thin film may be amorphous silicon oxynitride in which oxygen is 4 to 64 atomic%, nitrogen is 3 to 56 atomic%, and the sum of the composition of oxygen and nitrogen is 75 atomic% or less. It is preferable from the relationship between the barrier and 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 silicon oxide-based thin film is not particularly limited. However, if the thickness is too large, the silicon oxide-based thin film is easily cracked, and if the thickness is too small, the gas barrier effect is small. ５０50 nm.

If necessary, immediately before forming the silicon oxide-based thin film, the polyolefin film may be subjected to a surface treatment to remove dirt and deposits on the surface.

In the present invention, the protective layer is a layer for protecting the barrier layer, and is also a polyolefin film. Polyolefin film as a protective layer is rigid,
It is preferable to use linear low-density polyethylene, low-density polyethylene, medium-density polyethylene, propylene random copolymer, and propylene block copolymer in terms of transparency and heat sealability. Although the thickness of these protective films is not particularly limited, it is 5 to 500 μm, preferably 10 to 2 μm.
00 μm.

In the present invention, the adhesive resin for laminating the gas barrier layer and the protective layer is preferably a polyolefin modified with an unsaturated carboxylic acid or a derivative thereof. 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.

In the present invention, a coating layer may be formed on the gas barrier layer so that the adhesive resin adheres well to the polyolefin film as the gas barrier layer. When a silicon oxide-based thin film is formed on the gas barrier layer, it is preferable to form an adhesive resin and a silicon oxide-based thin film that exhibit good adhesion to both. Inorganic substances such as zinc oxide, alumina, titanium oxide, and indium tin oxide (ITO) are preferable because elution of organic substances must be suppressed for use as an infusion container. One or more of these inorganic substances may be used.

The coating layer is formed by vacuum deposition of the above inorganic substance,
It is formed on a polyolefin film serving as a gas barrier layer (if a silicon oxide-based thin film is formed, on a silicon oxide-based thin film) by a technique such as sputtering or CVD. The thickness of the coating layer is 1 to 100 nm, preferably 2 to 100 nm, since a certain thickness is required for uniform coating.
It is preferably about 20 nm.

The above-mentioned adhesive layer is not used as an independent layer, but may be a protective layer in which the components of the adhesive layer are kneaded.

The laminate of the present invention is a gas barrier layer (polyolefin film / inorganic layer) in a polyolefin film laminate in which a polyolefin film / inorganic layer / coating layer / adhesive layer / protective film is sequentially laminated, or A protective film may be laminated after laminating a large number of inorganic layers formed on both sides (inorganic layer / polyolefin film / inorganic layer) via an adhesive layer.

[0025]

EXAMPLES Next, a method for producing a polyolefin laminate will be described based on examples. Note that the present invention is not limited to this. (Example 1) 13.56 MH on a cyclic polyolefin film (trade name: Apel, Mitsui Chemicals, Inc.) having a thickness of 20 μm and a TMA represented by the chemical formula (I) at 80 ° C.
A silicon oxynitride thin film was formed by sputtering using a high-frequency power source of z. 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.
On this silicon oxynitride thin film, an ITO layer having a thickness of 5 nm was formed as a coating layer by sputtering using indium tin oxide (ITO) as a target.

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 0.2% was used. 965 linear polyethylene having a density of 0.965, containing 15% by weight of a linear polyethylene, 10% by weight of an ethylene-α-olefin copolymer having a density of 0.850, and 2.2% by weight of a maleic ester. Weight percent, and extruded the resin modified in an extruder as an adhesive layer so as to have a thickness of 20 μm, followed by laminating a 100 μm thick polyethylene film obtained in advance by casting to form a protective film layer. The obtained polyolefin laminate (J1) was obtained.

Example 2 A cyclic polyolefin film (trade name: Apel, Mitsui Chemicals, Inc.) having a thickness of 130 μm and having a TMA of 125 ° C. represented by the chemical formula (I) was used, and titanium oxide (film thickness) was used as a coating layer. A polyolefin laminate (J2) was produced in the same manner as in Example 1 except that 5 nm) was used.

Example 3 A silicon oxide (SiO _x ) thin film was formed on the cyclic polyolefin film used in Example 1 by sputtering using a 13.56 MHz high frequency power supply. The film was formed by reactive sputtering with oxygen using silicon having a purity of 99.99% as a target. The pressure during film formation is 0.2 Pa, the input power is 120
A film was formed with W for 5 minutes to form a 30-nm-thick SiO _x thin film. An ITO layer having a thickness of 5 nm was formed as a coating layer on the SiO _x thin film by sputtering using indium tin oxide (ITO) as a target. Further, an adhesive layer was formed thereon by extrusion lamination in the same manner as in Example 1, and then a 100-μm-thick polyethylene film was adhered to obtain a polyolefin laminate (J3) having a protective film layer.

Example 4 13.5 on both sides of the cyclic polyolefin film used in Example 1 in the same manner as in Example 1.
A silicon oxynitride thin film was formed to a thickness of 30 nm on each surface by sputtering using a 6 MHz high frequency power supply. On each of these thin films, an ITO layer was formed as a coating layer on each surface by 5 nm under the same conditions as in Example 1.

Further, Example 1 was placed on these coating layers.
Each of the adhesive layers was formed by extrusion lamination in the same manner as described above, and then a 100 μm-thick polyethylene film was adhered to each surface to obtain a polyolefin laminate (J4) as a protective film layer.

(Comparative Example 1) Polyethylene terephthalate (PE) having a thickness of 38 μm was used as a film of the gas barrier layer.
T) Example 1 except that a film (trade name: Lumirror, Toray Industries, Inc.) was used and no coating layer was formed.
A polyolefin laminate (H1) was prepared in the same manner as described above.

Comparative Example 2 An unstretched polypropylene film having a thickness of 300 μm (C
PP), and a polyolefin laminate (H2) was prepared in the same manner as in Example 3 except that no coating layer was formed.
It was created.

Table 1 summarizes the evaluation results of the physical properties of the polyolefin laminates shown in Examples and Comparative Examples. The evaluation method of the laminated body was implemented by the following method. Oxygen gas permeability is M
Using a gas permeation measuring device manufactured by OCON, 40 ° C, 0 ° C
% RH. The water vapor transmission rate was measured under the conditions of 40 ° C. and 90% RH using a gas transmission measuring device manufactured by MOCON. Light transmittance and b value (ratio of yellow and blue)
Was measured by Hitachi spectrophotometer U-3400. Light transmittance was measured at a wavelength of 450 nm.

[0034]

[Table 1]

Further, after the polyolefin laminates of J1, 2, 3, 4, H1, and 2 were steam-sterilized at 115 ° C. for 40 minutes, the peel strength was measured. The peel strength of the polyolefin laminate was measured at a size of 1.5 cm in width and 10 cm in length, and measured at a pulling speed of 50 mm / min. J
In all of the laminates 1, 2, 3, 4, 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 Japanese Pharmacopoeia Pharmaceutical Injection Plastic Container Test Method. J1,
Tests were performed on 2, 3, 4, H1, and 2 gas barrier film laminates each having an area of 600 cm ² . 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 its weight was measured.
The results are shown in Table 2.

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

[0038]

[Table 2]

[0039]

As described above, the polyolefin laminate produced according to 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 a liquid such as an infusion is packaged. Since there are few substances, it can be suitably used as a medicine packaging container for infusion and the like.

[Brief description of the drawings]

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

[Explanation of symbols]

 1 Polyolefin film as gas barrier layer 2 Silicon oxide thin film 3 Coating layer 4 Adhesive layer 5 Polyolefin film as protective layer

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 23/02 C08L 23/26 23/26 A61J 1/00 331A 331C F-term (Reference) 4F100 AA12C AA19D AA20 AA20C AA21D AA25D AA33D AK01B AK02 AK02A AK03A AK03B AK03G AK04 AK04A AK06 AK62 AK62G AK63 AK66G AL01A AL03G AL05B AL07G AS00B BA02 BA04 BA06 BA07 BA10A BA10B EC01 EC012 EH17 EH172 EH66 EH662 GB16 GB66 JA05A JD02A JD03 JD04 JD05 JL12B JN01C YY00A 4J002 BB031 BB041 BB051 BB141 BB151 BB202 BB212 GG02 4J100 AA02P AA03P AR21Q CA01 CA04 CA31 HA57 HC29 HC30 HC50 HC63 JA58

Claims (15)

[Claims] 1. A polyolefin film laminate comprising at least a gas barrier layer composed of a polyolefin film and a protective layer composed of a polyolefin film, wherein the laminate has the following physical properties. Light transmittance is 55% or more Hue b value is 5 or less Oxygen gas transmittance measured at 40 ° C. in a dry atmosphere is 50 cc / m ² · day · atm or less Water vapor transmittance is 2 g / m ² · day · atm Less than 2. The polyolefin laminate according to claim 1, wherein a transparent silicon oxide-based thin film is formed on at least one surface of the polyolefin film serving as a gas barrier layer. 3. The polyolefin laminate according to claim 2, wherein the silicon oxide-based thin film is silicon oxynitride containing a nitrogen element. 4. An amorphous silicon oxynitride 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 polyolefin laminate according to claim 3. 5. The softening temperature (TMA) of a polyolefin film as a gas barrier layer is 70 ° C. or higher.
5. The laminate according to any one of items 4 to 4. 6. The polyolefin laminate according to claim 1, wherein the polyolefin film serving as the gas barrier layer has a copolymer structure of cycloolefin and α-olefin. 7. Cycloolefin and α-cycloolefin
The polyolefin laminate according to claim 6, wherein the olefin copolymer is represented by the following formula (I). Embedded image 8. A silicon oxynitride thin film / a coating layer having good adhesion to an adhesive resin / an adhesive layer composed of an adhesive resin / a protective layer composed of a polyolefin film are sequentially formed on a polyolefin film serving as a gas barrier layer. A polyolefin laminate according to any one of claims 1 to 7. 9. A coating layer comprising zinc oxide, aluminum oxide, titanium oxide and indium tin oxide (IT).
The polyolefin laminate according to claim 8, wherein the polyolefin laminate comprises one or more members selected from O). 10. The polyolefin laminate according to claim 8, wherein the adhesive resin is a modified polyolefin that is an unsaturated carboxylic acid or a derivative thereof. 11. The polyolefin laminate according to claim 10, wherein the modified polyolefin is ethylene homopolymer or an ethylene-α-olefin random copolymer containing 10 mol% or less of other α-olefin. 12. The polyolefin laminate according to claim 10, wherein the modified polyolefin is propylene homopolymer or a propylene-α-olefin random copolymer containing 10 mol% or less of other α-olefin. 13. The polyolefin laminate according to claim 1, wherein the polyolefin film of the protective layer is a polyolefin film into which an adhesive resin has been kneaded. 14. The polyolefin laminate according to claim 1, which is used for a chemical container. 15. The polyolefin laminate according to claim 1, which is for an infusion container.