JPH0258570A - Packaging material for deoxidation agent - Google Patents

Abstract

PURPOSE:To provide a packaging material for deoxidation agent, made of a film composed of graft copolymer resin of an olefinic polymer and a polyorganosiloxane and usable in contact with a liquid or a liquid-containing substance for a long period without causing the lowering of gas-permeability and the permeation of the liquid. CONSTITUTION:A film is produced from a graft copolymer resin produced by the graft polymerization of 100 pts.wt. of an olefinic polymer (e.g., polyethylene or polypropylene) and 50-300 pts.wt. of a polyorganosiloxane. As an alternative method, the film is produced from a resin mixture produced by mixing 100 pts.wt. of the above graft copolymer and 10-1,000 pts.wt. of an olefinic polymer. If necessary, the film is laminated with a gas-permeable sheet composed of paper, nonwoven cloth, etc.

Description

[Detailed Description of the Invention] [Industrial Application Field] Each of the present inventions particularly relates to a liquid substance such as a liquid or a viscous substance, a certain one.
The present invention relates to a packaging material for an oxygen absorber used to prevent oxidation of substances containing the above-mentioned liquid substances.

[Conventional technology]

Antioxidants used for products that require oxidation prevention are usually used in the form of a package in which an oxygen scavenger, which is an oxygen absorber, is wrapped in a breathable packaging material. Oxygen in the atmosphere in which the oxygen agent package is present is adapted to be absorbed by the oxygen absorbent in the package.

When the oxygen scavenger comes into contact with moisture or oily components,
Since the oxygen absorbing ability of the oxygen absorber decreases, which causes deterioration, when the package is used in contact with moisture or oily components, moisture or moisture from the packaging material used to package the oxygen absorber may be used. In order to prevent oil from penetrating, the surface of the packaging material is coated with a water and oil repellent.

[Problem to be solved by the invention]

However, when the packaging material comes into contact with an object containing water, alcohol, oil, etc. for a long time, the air permeability of the packaging material may be inhibited or/or the liquid may pass through the packaging material. Penetrates the oxygen absorber inside the package,
Not only does the oxygen absorbing ability of the oxygen absorber decrease, but also the reaction between the oxygen absorber and the liquid component may generate a strange odor. In reality, it cannot be used as a packaging material for pharmaceuticals.

In contrast, each of the present inventions provides a liquid substance such as a liquid or a viscous substance,
Alternatively, when used in contact with the above substance to prevent oxidation of a solid substance containing the liquid substance,
The object of the present invention is to provide a packaging material for an oxygen absorber that does not have the disadvantages of the conventional packaging materials for oxygen absorbers described above.

[Means to solve the problem]

The packaging material for oxygen scavengers invented by Mizui I consists of a single film made of a graft copolymer resin obtained by graft polymerizing polyorganosiloxane to an olefin polymer. It is.

In addition, the packaging material for oxygen scavengers of the invention of Mizui 2 is made of a mixed resin of a graft copolymer resin obtained by graft polymerizing polyorganosiloxane to an olefin polymer and an olefin resin. It consists of a single film that has been formed into a film.

Furthermore, the packaging material for an oxygen absorber according to the invention of Mizuo 3 includes the single film of the invention of Suiyo 1 or the second invention, paper,
It consists of a laminated sheet with a separate breathable sheet made of 90% non-woven fabric, perforated resin film, etc.

In addition, in the packaging material for an oxygen scavenger according to the invention of Suihiro 4, the olefin polymer in the graft copolymer resin according to the inventions of Suihiro 1 to 3 is polyethylene, polypropylene, poly4-methylpentene, , or ethylene with acrylic acid, methyl acrylate, ethyl acrylate, methacrylic acid, methyl methacrylate, vinyl acetate, butene, pentene, hexene, heptene.

It consists of a single film or a dipping layer made of one or more ethylene copolymers made of octene or 4-methylpentene-1.

Furthermore, the packaging material for the oxygen absorber of the fifth invention is:
The olefin resin in the mixed resin of the graft copolymer resin and olefin resin in the second to fourth inventions is polyethylene, polypropylene, poly4-methylpentene-1, or ethylene, acrylic acid, acrylic One or more ethylene copolymers such as methyl acrylate, ethyl acrylate, methacrylic acid, methyl methacrylate, vinyl acetate, butene, pentene, hexene, heptene/octene, 4-methylpentene-1, etc. It consists of a single film or a laminated sheet.

The graft copolymer resin used in the packaging material of the sphagnum moss invention is obtained by graft polymerizing polyorganosiloxane to an olefin polymer. It is obtained by graft copolymerizing a polyorganosiloxane having unsaturated bonds with an olefin polymer.

In addition, the ratio of the olefin polymer to the polyorganosiloxane in the graft copolymer resin is determined based on the relationship between the oxygen permeability and weldability of the resulting film. The amount of Silxa is approximately 50 to 300 parts by weight.

Furthermore, the ratio of the graft copolymer resin and the olefin polymer in the mixed resin is such that the oxygen gas permeability of the polyorganosiloxane component and the thermal welding performance of the polyolefin resin component in the mixed resin are balanced. Therefore, it is necessary to prepare the graft copolymer resin so that it exhibits the same properties as the graft copolymer resin, although it varies depending on the amount ratio of the polyorganosiloxane component in the graft copolymer resin used in the mixed resin. The amount of the olefin polymer is about 10 to 1000 parts by weight per 100 parts by weight of the combined material.

In the packaging material of the third to fifth inventions, when the packaging material is a laminated sheet with a separate breathable sheet made of paper, 90% nonwoven fabric, perforated resin film, etc.
A graft copolymer resin or a mixed resin of graft copolymer resins may be extruded and laminated onto the separately manufactured breathable sheet, or a ready-made material may be laminated with a graft copolymer resin or a mixed resin of graft copolymer resins. The film can be laminated by a welding method to a separately manufactured breathable sheet, or a ready-made film made of a graft copolymer resin or a mixed resin of graft copolymer resin and a separately manufactured breathable sheet can be laminated. This can be easily obtained by partially adhering the sheets to each other using an adhesive that is partially applied.

The oxygen absorbers packaged by the packaging material of the Sphagnum moss invention are usually common oxygen absorbers, such as sulfites, bisulfites, thiosulfates.

Dithionite, hydroquinone, catechol.

resorcinol, pilgalur, gallic acid, p-ngalit,
Ascorbic acid, ascorbate.

Inascorbic acid, inascorbate.

Sorbose, glucose, lignin, dibutylated hydroxytoluene, butylated hydroxyanisole, ferrous salt,
iron powder, etc., or the oxygen absorbent and carbon dioxide gas generating agent,
It is a mixture with a carbon dioxide absorbent, and the oxygen absorbent can of course be packaged directly, for example, in a separate breathable sheet made of paper, non-woven fabric, perforated resin film, etc. Therefore, it can also be used as a packaging material for further packaging the oxygen absorber package in which the oxygen absorber is packaged. The specific structure of the material will be explained based on examples.

Example 1 Graft copolymer resin r 5P-100 obtained by graft polymerizing polyorganosiloxane to an olefin polymer consisting of ethylene-methyl methacrylate copolymer:
Susumu Chemical Industry■, 7Licorn content 60wt, %"50
parts by weight, ethylene methyl methacrylate copolymer resin "
Acrift WH3031, methyl methacrylate content 1
A spunbond nonwoven fabric made of polyester fibers was extruded at a temperature of 270° C. by extruding a resin mixture containing 50 parts by weight of 8wt%.

Packaging material for oxygen scavenger, which is an embodiment of the present invention, consisting of an M-layer sheet extruded and laminated on one side surface of 3og/F;/J and having a resin film layer with a thickness of 25 μm (1
) was obtained.

The oxygen permeability of the packaging material (1) is 41,000.
cc/i, 24Hr (25°C, 100%).

Further, by using the packaging material (1), a 20×2 bag-like body whose inner peripheral surface layer is formed of a resin film layer made of the packaging material, and in which 5 g of iron powder is sealed.
An oxygen absorber package rIJ of 0.0 mm was obtained by a thermal welding method.

Comparative Example 1 Ethylene-methyl methacrylate copolymer resin “Acrift WH3031, methyl methacrylate content 18wt,
%'' at an extrusion temperature of 270%, a spunbond nonwoven fabric made of polyester fiber-rUnif-force@: 7
! J-/97.20307WTD, basis weight 30g/
Comparative packaging material (a) for an oxygen scavenger was obtained, which consisted of a laminated sheet having a resin film layer of 25 μm in thickness by extrusion lamination on one surface of “d”.

In addition, the packaging material for the oxygen absorber for the above comparison $4(a)
The oxygen permeability is 9200cc/rrt ・24)
(r (25°C, 100%).

Further, by using the packaging material R(a), a bag-like body whose inner circumferential surface layer is formed of a resin film layer made of the packaging material, and 5 g of iron powder is sealed inside the 20X
A 20-meter oxygen absorber package "1" was obtained by a heat welding method.

Example 2 Graft copolymer resin rSP-300 obtained by graft polymerizing polyorganosiloxane to polyethylene: Sumima Kagaku Kogyo ■, free corn content 40 wt, %J 50
A mixed resin of 50 parts by weight and 50 parts of low-density polyethylene resin "Sumiyoshi Kagaku: Sumiriki Seven", -705J, was extruded at a temperature of 290°C to form a core made of polyester and a sheath made of polyethylene. A non-woven fabric made of composite synthetic fibers with
Packaging material for oxygen scavenger (2), which is an embodiment of the present invention, consisting of a laminated sheet having a resin film layer with a thickness of 20 μm
I got it.

The oxygen permeability of the packaging material (2) is 37,000.
cc/n?・24Hr (25°C, 100%), but the oxygen permeability of a 20μ thick resin film made of low density polyethylene resin [Jumikagaku: Sumikasen L-7054 is 8200cc/rrl・24Hr (25°C)
, 100%).

Further, by using the packaging material (2), a bag-like body whose inner peripheral surface layer is formed of a resin film layer made of the packaging material, and 5 g of iron powder is sealed inside.
A 20 mm oxygen absorber package r[IJ was obtained by a heat welding method.

Example 3 Graft copolymer resin rSP-300 in which polyorganosiloxane was graft-polymerized to polyethylene: A blown film with a thickness of 30 µm was made from "Sumiman Kagaku Kogyo ■, silicone content 40 wt, %" as a film forming raw material. Packaging material for oxygen absorber which is an example product of the present invention (3
) was obtained.

The oxygen permeability of the packaging material (3) is 44,000.
cc/rrl, 24Hr (25°C, 100
%), but the oxygen permeability of a 30μ thick resin film made of low density polyethylene resin "Susumikasen L-705J" is 8900cc/n?・24Hr(
25°C, 100%) Furthermore, using the packaging material (3), iron powder is added inside.
An oxygen absorber package rfflJ consisting of a bag-like body of 20×20s+s+ in which G was enclosed was obtained by a heat welding method.

Comparative Example 2 One side surface is made of a commercially available non-woven fabric "Tyvek 1059B, basis weight 61 g/iJ, and the other side surface is made of a laminated sheet made of low density polyethylene. Oxygen absorber package consisting of a 20 x 20 bag-like body in which 5 g of iron powder is sealed inside with the resin layer (30μ) surface being the inner peripheral surface layer.
11'' was obtained by a thermal welding method.

After filling 200 m/m of a 1/1 mixture of water and alcohol into a self-supporting bag made of a laminated sheet, each of the oxygen scavenger packages in the above Examples and Comparative Examples was put in, and the head space was filled. A sealed package of 50 m/each was formed, and changes in the amount of dissolved oxygen (PPm) in the Moeki water/alcohol mixture at 25°C were measured.

The results are shown in a table.

In addition, rust of iron powder was leached into the liquid in the oxygen absorber package of Comparative Example 2 after 7 days.

[Action and effect of the invention]

The packaging material for oxygen scavengers invented by Mizui 1 consists of a single film made of a graft copolymer resin obtained by graft polymerizing polyorganonoloxane to an olefin polymer. It is.

In addition, the packaging device 14t1 for oxygen scavenger invented by Mizui 2 is as follows:
A graft copolymer resin obtained by graft polymerizing a polyorganosiloxane to an olefin polymer;
A film is formed from a mixed resin with an olefin resin (・
It consists of a single film.

Furthermore, the packaging material for an oxygen absorber according to the invention of Mizuo 3 includes the single film of the invention of Suiyo 1 or the second invention, paper,
It is made of a laminated sheet with a separate breathable sort made of non-woven fabric, perforated resin film, etc.

In addition, in the packaging material for an oxygen scavenger according to the invention of Suihiro 4, the olefin polymer in the graft copolymer resin according to the inventions of Suihiro 1 to 3 is polyethylene, polypropylene, poly4-methylpentene, , or ethylene with acrylic acid, methyl acrylate, ethyl acrylate, methacrylic acid, methyl methacrylate, vinyl acetate butene, pentene, hexene, heptene.

It consists of a single film or a laminated sheet made of one or more ethylene copolymers consisting of octene and 4-methylpentene-1.

Furthermore, the packaging material for the oxygen absorber of the fifth invention is:
The olefin resin in the mixed resin of the graft copolymer resin and olefin resin in the second to fourth inventions is polyethylene, polypropylene, poly4-methylpentene-1, or ethylene, acrylic acid, acrylic Methyl acrylate, ethyl acrylate, methacrylic acid, methyl methacrylate, vinyl acetate, butene, pentene, hexene, heptene, octene, or 4-methylpentene-
It consists of a single film or a laminated sheet made of one or more of the ethylene copolymers consisting of (1) and (1).

Therefore, the packaging material for oxygen scavenger of the actual invention has the oxygen gas permeability and water/oil repellency of the polyorganosiloxane graft copolymerized with the olefin polymer, and the olefin polymer. It is achieved by balancing the heat weldability of the packaging material with the heat weldability of the packaging material, and even if it comes into contact with an object containing water, alcohol, oil, etc. for a long time, the air permeability of the packaging material may be inhibited, or the liquid It works extremely well as a packaging material for oxygen absorbers as it can be left in contact with liquid materials for long periods of time without allowing objects to pass through the packaging material and penetrate into the oxygen absorber inside the package. It is something that plays.

Patent applicant: Dai Nippon Printing Co., Ltd. Representatives: Rikichi Ichikawa, Kiyoko Arai

Claims (5)

[Claims] (1) A packaging material for an oxygen absorber comprising a film made of a graft copolymer resin of an olefin polymer and a polyorganosiloxane. (2) A packaging material for an oxygen absorber comprising a film made of a mixed resin of a graft copolymer resin of an olefin polymer and a polyorganosiloxane and an olefin resin. (3) An oxygen absorbing device comprising a laminated sheet of the film according to claim 1 or 2 and a breathable sheet made of paper, nonwoven fabric, split cloth, perforated resin film, etc. Packaging materials for drugs. (4) The olefin polymer in the copolymer resin with polyorganosiloxane is polyethylene, polypropylene, poly4-methylpentene-1, or ethylene, acrylic acid, methyl acrylate, ethyl acrylate,
Claims 1 to 1 are at least one ethylene copolymer consisting of methacrylic acid, methyl methacrylate, vinyl acetate, butene, pentene, hexene, heptene, octene, or 4-methylpentene-1. A packaging material for an oxygen absorber according to any one of item 3. (5) The olefin resin in the mixed resin of the graft copolymer resin and the olefin resin is polyethylene, polypropylene, poly4-methylpentene-1, or
An ethylene copolymer consisting of ethylene and acrylic acid, methyl acrylate, ethyl acrylate, methacrylic acid, methyl methacrylate, vinyl acetate, butene, pentene, hexene, heptene, octene, or 4-methylpentene-1. A packaging material for an oxygen absorber according to any one of claims 2 to 4, which is one or more types.