JPH11285520A - Film for chemical container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce the gas permeability and to enhance the preservation property of chemicals such as an infusion solution, by forming an inorganic compound membrane on one surface of a plastic film so that physical properties such as an oxygen permeability, a moisture permeability on a light transmissivity has a specified value and also using specified amorphous silicon oxidenitride in the inorganic compound. SOLUTION: The chemical container film to be the material of an infusion container for containing and preserving the infusion such as a glucose liquid, a physiological salt solution and a Ringer solution is formed by arranging the inorganic compound membrane on one surface of the plastic film so that the film has a oxygen permeability of <=1 cc/m<2> .24 h.atm, a moisture permeability of 1 g/m<2> .24 hr, the light transmissivity of >=80% and a hue (b) value of <=5. the gas permeability is reduced and the preservation property of the chemicals such as the infusion is enhanced by the film. Besides, amorphous oxidation- nitrided silicon having an oxygen concentration of 4-64 atom %, a nitrogen concentration of 3-56 atom % and also the sum of the concentration is <=75 atom % is favorable as the inorganic compound to be used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a material for a medicine container, especially for an infusion container for storing and storing infusion solutions such as glucose solution, physiological saline, Ringer's solution, protein solution, amino acid solution, plasma, artificial dialysis agent, and fat agent. And a film for a chemical container.

[0002]

2. Description of the Related Art Conventionally, glass containers have been frequently used as chemical containers, particularly, infusion containers. However, in recent years, plastics have been increasingly used because they are easily broken and heavy, which increases transportation costs.

[0003] Plastics do not always have sufficient gas barrier properties, in particular, oxygen barrier properties and water vapor barrier properties. Therefore, there has been a problem that the infusion preservability of plastic infusion containers is inferior to that of glass. In order to solve this problem, attempts have been made to create an infusion container by selecting various materials having high gas barrier properties.However, in the infusion container made of these materials, material components are eluted into the infusion. There was a problem such as doing.

Infusion containers are required to have not only gas barrier properties but also good physical properties such as pinhole resistance, drop strength and compressive strength. For this reason, resins having excellent sealing properties and excellent impact resistance, such as polyethylene and polypropylene, are used. For example, Japanese Patent Application Laid-Open No. H3-4870 discloses that a ceramics film is provided on one or both sides of a plastic film such as polyethylene or polypropylene. An infusion container using a transparent laminated film provided with a thin layer is disclosed. However, this infusion container does not have sufficient gas barrier properties.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and has been made to reduce gas permeability and enhance the preservability of chemicals such as infusions, and to improve transparency, sealability and impact resistance. Provided is a film for a chemical container used for producing an infusion container or the like having excellent properties.

[0006]

The film for a chemical container according to the present invention is obtained by forming an inorganic compound film on at least one surface of a plastic film and has the following physical properties. (1) Oxygen permeability is 1 cc / m ² · 24 hr · atm or less; (2) Moisture permeability is 1 g / m ² · 24 hr or less; (3) Light transmittance is 80% or more; (4) Hue b value is 5 The inorganic compound has an oxygen concentration of 4 to 64 atomic%, a nitrogen concentration of 3 to 56 atomic%, and a sum of oxygen and nitrogen concentrations of 7 to
It is preferably amorphous silicon oxynitride containing 5 atomic% or less. Further, according to the present invention, there is provided a film for an infusion container comprising the above film.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The chemical container according to the present invention, in particular, the film for an infusion container will be described in detail below.

The chemical container film according to the present invention is obtained by forming an inorganic compound film on at least one surface of a plastic film. Further, the inorganic compound,
It is preferably amorphous silicon oxynitride containing oxygen and nitrogen at an atomic concentration described later.

<Plastic Film> The plastic film substrate used in the present invention is a film made of a resin having excellent transparency, sealability and impact resistance. Examples thereof include a polyester film such as polyethylene terephthalate; Polypropylene, poly 1
-Polyolefin films such as butene; polystyrene films; polyamide films; polycarbonate films; polyacrylonitrile films, and the like.

The plastic film substrate may be a stretched film or an unstretched film, but in order to satisfy the light transmittance of the film for a chemical container of the present invention, the film substrate has a light transmittance of at least 80% or more. You need to use something. In the present invention, a film thickness of 0.01 to 1 mm is preferably used. Further, it is preferable that the smoothness of the surface of the plastic film is as good as possible. This is because if the surface smoothness is poor, the gas barrier properties of the film for a chemical container according to the present invention may be reduced. The surface smoothness is preferably such that Rmax (the maximum value of the difference between peaks and valleys, measured by a surface roughness meter) representing the surface roughness is 50 nm or less.
It is preferably 0 nm or less.

Further, in order to enhance the adhesion of the inorganic compound film described later to the surface of the plastic film substrate, the surface of the substrate may be subjected to cleaning treatment such as cleaning for degreasing and dewatering, if necessary, and vacuum container. A known process such as a plasma process using an inert gas such as He, an oxygen gas, or the like may be performed therein.

<Inorganic Compound Film> As the inorganic compound film of the present invention, an amorphous silicon oxynitride film is preferable. The amorphous silicon oxynitride film referred to in the present invention is a glassy thin film containing oxygen and nitrogen and containing silicon as a main component. The ratio of the component elements in the film can be continuously changed depending on the film forming conditions, and the properties of the film change accordingly. In order to exhibit excellent gas barrier properties as compared with films such as silicon oxide films and aluminum oxide films, an oxygen concentration of 4 to 64 atomic%, a nitrogen concentration of 3 to 56 atomic%, and a sum of oxygen and nitrogen concentrations of 75 atoms % Or less of amorphous silicon oxynitride. A film having this elemental composition range has excellent barrier properties against oxygen and water vapor and shows high light transmittance.

<Method for Forming Amorphous Silicon Oxynitride Film> In order to form the above-mentioned amorphous silicon oxynitride film, a source gas containing Si is used. Examples of the raw material gas containing Si and hydrogen include silane, disilane, and the like. These are introduced into a vacuum vessel together with a nitrogen-containing gas such as ammonia or nitrogen gas and an oxygen gas, and generate plasma to generate a plastic gas. An amorphous silicon oxynitride film is formed on the film. Organic silicon compounds such as tetramethylsiloxane, hexamethyldisiloxane, and trimethylmethoxysilane are also used as the source gas containing Si. These are introduced into a vacuum vessel as a mixed gas of nitrogen gas and oxygen gas, and generate plasma to form a silicon oxynitride film on a plastic film.

Means for exciting the above-mentioned raw material gas introduced into the vacuum vessel by plasma include, for example, a method of applying a direct current to decompose a plasma; a method of applying a high frequency to decompose a plasma; Decomposition method; plasma decomposition method by electron cyclotron resonance; and thermal decomposition method by heating with a hot filament. In the present invention, since a plastic film is used as the substrate, it is desirable to form the film at a low temperature, and a plasma CVD method applying a direct current or a microwave CVD method applying a high frequency is preferable.

As a method for forming an amorphous silicon oxynitride film, a physical vapor deposition method such as direct current sputtering, high frequency sputtering, or ion beam sputtering can be employed. In this case, an inorganic compound suitable for the film composition is used as the target material.

It is important that the thickness of the amorphous silicon oxynitride film is in a range that does not impair transparency while ensuring gas barrier properties. In the present invention, the thickness is preferably 10 to 300 nm, more preferably 20 nm. １００100 nm. further,
If the thickness is the same, it is preferable to provide a silicon oxynitride film separately on both sides in terms of gas barrier properties. For example, thickness 200n
The gas barrier property tends to be higher when a film having a thickness of 100 nm is provided on both surfaces than when a film having a thickness of m is provided on one surface.

In the above-mentioned amorphous silicon oxynitride film, iron, nickel, chromium, titanium, magnesium, aluminum, indium, zinc, tin, antimony, tungsten, molybdenum are used as long as the object of the present invention is not impaired. , Copper and the like. Further, carbon, fluorine or hydrogen can be contained for the purpose of improving the flexibility of the film. The composition of the silicon oxynitride film can be analyzed using X-ray photoelectron spectroscopy, X-ray microanalysis, Auger electron spectroscopy, or Rutherford backscattering.

Hereinafter, a sputtering apparatus used for forming an amorphous silicon oxynitride film will be described with reference to the drawings. FIG. 1 shows an apparatus 1 for forming a silicon oxynitride film.
It is a schematic diagram which shows an example. In FIG. 1, 1 is a vacuum vessel,
2 is a cooling roll, 3 is a base film, 4 is a glow discharge device, 5 is a target device, 6 is an unwinding roll, 7 is a winding roll, and 8 is a transport roll.

The formation of the silicon oxynitride film by a sputtering method is performed by a method in which the surface of the base film is subjected to an oxygen glow treatment and then subjected to DC sputtering. As a film forming operation, first, a plastic film substrate is placed on the cooling roll 2 in the vacuum container 1, and then the inside of the vacuum container is set to a high vacuum. The degree of vacuum at this time is preferably 0.2 Pa or less in order to reduce the influence of impurity contamination on the film due to the residual impurity gas. Next, oxygen is introduced to a predetermined pressure,
A predetermined direct current is applied to generate glow discharge, and the substrate film surface is exposed to oxygen glow discharge. At this time, the pressure of the oxygen gas is 0.5 to 15 Pa, the current is 0.2 to 0.5 A,
The voltage is preferably between 500 and 2000V.

Next, a silicon oxynitride film is formed by DC sputtering. After evacuation of the vacuum vessel, argon gas and oxygen gas are introduced so as to have a predetermined pressure, and nitrogen gas such as nitrogen gas and ammonia are further introduced until the pressure becomes a predetermined pressure. The introduction amount of the oxygen and nitrogen generation gas differs depending on the ratio of oxygen and nitrogen in the target silicon oxynitride film. The pressure in the vacuum vessel after introducing all the gases is usually 0.2 to 10 Pa.

Next, a predetermined direct current is applied to generate a plasma of the mixed gas. DC current is 5-20A, voltage 50
It is preferably in the range of 0-2000V. The plasma of the mixed gas collides with a target made of metallic silicon, and the silicon atoms struck out by the impact of the plasma react with oxygen and nitrogen to deposit on the surface of the base film to form a silicon oxynitride film.

The temperature of the substrate film rises because the plasma-converted raw gas atoms collide with the substrate film.
In order to prevent the base film 3 from being deteriorated by this, it is preferable to keep the base film 3 at or below its glass transition point. This temperature control is realized by circulating a liquid cooled to a predetermined temperature through a cooling roll 2 which is a support of the base film 3 and controlling the cooling roll. As the liquid to be circulated, water, ethylene glycol (antifreeze), alcohols, and liquid nitrogen, liquid helium, and the like are preferably used when a lower temperature is required. As another cooling method, a method of circulating a gas may be used, but a method of circulating a liquid is preferable because of its large heat capacity.

<Film for Chemical Container> The film for a chemical container of the present invention comprises: (1) oxygen permeability of 1 cc / m ² · 24 hr · atm or less; (2) moisture permeability of 1 g / m ² · 24 hr or less; Because of its low gas permeability, it also has heat resistance because the inorganic compound is formed as a film, and since it has excellent flexibility as a film, it is suitable as a material for making a chemical container for transporting liquid. is there.

On the formed amorphous silicon oxynitride film,
Further, it is preferable to laminate a transparent plastic film having the same or different heat sealing property from that of the base film, since it is possible to prevent a film defect from occurring during processing such as heat sealing. Examples of the transparent plastic film having excellent heat sealing properties include polyolefin resin films such as polyethylene and polypropylene. In addition, as a laminating method, a method of heating a base film on which an inorganic compound film is formed, extruding and laminating a film for lamination so as to sandwich the inorganic compound, and applying an adhesive on the inorganic compound film Then, a method of attaching a film for lamination or the like can be adopted. The thickness of the film for a chemical container after lamination is 5 to 1000 μm, preferably 10 to 700 μm,
More preferably, it is 10 to 300 μm.

Further, the film for a medicine container of the present invention has (3) a light transmittance of 80% or more; (4) a hue b value of 5 or less; It is easy to identify, and it is possible to easily find a change in the contents due to the entry of a foreign substance during storage of the medicine.

Further, since the drug container obtained by using the film of the present invention has the above-mentioned physical properties, infusion of glucose, physiological saline, Ringer's solution, protein solution, amino acid solution, plasma, artificial dialysis agent, fatty agent, etc. Has excellent long-term storage stability. In addition, since it is lightweight, it is excellent in the transportability of contents.

[0027]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples.

Example 1 A 50 μm-thick polyethylene terephthalate film (registered trademark “Lumirror” made by Toray Industries, Inc., highly transparent type) was placed on a roll in a vacuum vessel 1 shown in FIG. The pressure was reduced to 0.0133 Pa. Oxygen gas is introduced into the glow discharge device 4 to reduce the pressure to 1P.
The current was set to a, and a direct current of 0.5 A and a voltage of 1000 V was applied to perform glow discharge treatment. Next, as a source gas, argon was set and introduced at 82 cc / min and nitrogen at 56 cc / min, and the pressure in the reaction chamber was set at 0.3 Pa. Using a single crystal of Si as a target, a direct current of 7 A and 1000 V was applied. The film was formed while winding the film at a speed of 0.9 m / min. The film thickness at this time was 48 nm. The composition of the film was analyzed using X-ray photoelectron spectroscopy. As a result, the film was a silicon oxynitride film containing 44 atomic% and 13 atomic% of nitrogen and oxygen, respectively. As a result of measuring the surface of the substrate film using an atomic force microscope (AFM), the maximum height difference Rmax was 17 nm (measurement range: 5 μm × 5 μm).

Example 2 A 50 μm thick polyethylene terephthalate film (“Lumirror highly transparent type” manufactured by Toray Industries, Inc.) was placed on a roll in a vacuum vessel 1 shown in FIG. The pressure was reduced. Oxygen gas was introduced into the glow discharge device 4, the pressure was set to 1 Pa, and a DC current of 0.5 A and a voltage of 1000 V was applied to perform glow discharge treatment. Next, as a source gas, argon was set and introduced at 82 cc / min and nitrogen at 56 cc / min, and the pressure in the reaction chamber was set at 0.3 Pa. Si as target
Using a single crystal, a direct current of 7 A and 1000 V was applied.
Film formation was performed while winding the film at a speed of 1.8 m / min. At this time, the film thickness was 24 nm. Also,
The composition of the film was analyzed by X-ray photoelectron spectroscopy. As a result, the film was a silicon oxynitride film containing 44 atomic% of nitrogen and 13 atomic% of oxygen.

Example 3 A 38 μm-thick polyethylene terephthalate film (“Lumirror highly transparent type” manufactured by Toray Industries, Inc.) was placed on a roll in the vacuum vessel 1 shown in FIG. The pressure was reduced. Oxygen gas was introduced into the glow discharge device 4, the pressure was set to 1 Pa, and a DC current of 0.5 A and a voltage of 1000 V was applied to perform glow discharge treatment. Next, as a source gas, argon was set and introduced at 82 cc / min and nitrogen at 56 cc / min, and the pressure in the reaction chamber was set at 0.3 Pa. Si as target
Using a single crystal, a direct current of 7 A and 1000 V was applied.
Film formation was performed on both sides while winding the film at a speed of 0.9 m / min. At this time, the thickness of each surface was 24 nm. The composition of the film was analyzed by X-ray photoelectron spectroscopy. As a result, the film was a silicon oxynitride film containing 44 atomic% of nitrogen and 13 atomic% of oxygen.

Comparative Example 1 A polyethylene terephthalate film having a thickness of 50 μm (“Lumirror highly transparent type” manufactured by Toray Industries, Inc.)

Comparative Example 2 Polyethylene terephthalate film having a thickness of 38 μm (“Lumirror highly transparent type” manufactured by Toray Industries, Inc.)

The films of the above Examples and Comparative Examples were evaluated by the following methods. (1) Moisture permeability Using a gas permeability measuring device manufactured by Mocon, 40
The measurement was performed under the conditions of ° C and 90% relative humidity. (2) Oxygen permeability Measured under an oxygen atmosphere at 23 ° C. using a gas permeability measuring device manufactured by Yanaco. (3) Light transmittance, haze (haze) and b value (ratio of yellow and blue) Integrating sphere haze meter (ND-1001 manufactured by Nippon Denshoku Co., Ltd.)
It measured using D). The wavelength of the measurement light is 550 nm.

[0034]

[Table 1]

[0035]

Since the film for a chemical container according to the present invention has excellent gas barrier properties, it is possible to provide a chemical container such as an infusion container having excellent long-term storage stability. further,
Since the film for a medicine container has high transparency and is lightweight, it is possible to easily find a change in the contents due to, for example, mixing of a foreign substance, and to provide an infusion container or the like excellent in transportability of a medicine solution. be able to. Further, it is also useful as a protective film for a solar cell utilizing this property.

[Brief description of the drawings]

FIG. 1 is a schematic view showing a sputtering apparatus for producing a laminated film according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Vacuum container 2 Cooling roll 3 Base film 4 Glow discharge treatment device 5 Target device 6 Unwinding roll 7 Take-up roll 8 Transport roll

Continued on the front page (72) Inventor Kazuo Yagi 2-1-1 Tangodori, Minami-ku, Nagoya-shi, Aichi Mitsui Chemicals, Inc.

Claims (3)

[Claims] 1. A film for a chemical container, comprising an inorganic compound film formed on at least one surface of a plastic film and having the following physical properties. (1) Oxygen permeability is 1 cc / m ² · 24 hr · atm or less; (2) Moisture permeability is 1 g / m ² · 24 hr or less; (3) Light transmittance is 80% or more; (4) Hue b value is 5 Less than; 2. The inorganic compound is an amorphous silicon oxynitride having an oxygen concentration of 4 to 64 at%, a nitrogen concentration of 3 to 56 at%, and a sum of oxygen and nitrogen concentrations of 75 at% or less. The film for a chemical container according to claim 1, wherein: 3. The container according to claim 1, wherein the medicine container is an infusion container.
Or the film for a chemical container according to 2.