JPH068971A - Film for deoxidizing agent and package - Google Patents

Abstract

PURPOSE:To obtain package good in oxygen gas permeability and water resisting property by forming the film for deoxidizing agent of a thermoplastic resin composition consisting of silicone resin, polyolefin-silicone copolymer, polyolefin, etc., as its components. CONSTITUTION:A package for filling therein deoxidizing agent D is formed of a multiple layer sheet comprising an upper layer A consisting of the film for deoxidizing agent, an intermediate layer B consisting of paper or plastic nonwoven fabric or fine-pored plastic membrane and, as required, a lower layer C consisting of a heat-sealable hole formed plastic film. In this case, the film for forming the upper layer A is formed of a thermoplastic resin composition consisting of silicone resin, polyolefin-silicone copolymer and polyolefin or polyamide as its components and containing silicone in an amount of at most 45%. In this way the package excellent in oxygen gas permeability and water resisting property is obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oxygen absorber film and an oxygen absorber package.

[0002]

2. Description of the Related Art In recent years, in the food field such as processed foods and fresh foods, it has become widespread to maintain the quality by controlling the storage environment such as the use of oxygen scavengers. A chemical for controlling the storage environment is used as a multi-layered package in which a transparent plastic film having an outermost layer subjected to perforation treatment or perforation treatment is laminated.

[0003]

[Problems to be Solved by the Invention] Currently, such a drug package is (1) water and oil resistant. (2) High transparency as the material used for the outermost layer because back printing is often performed. (3) Gas permeability is sufficiently high. (4) Fillability and sufficient strength. However, there are no conventional packages that fully satisfy all of these properties, and they have good gas permeability, especially oxygen gas permeability, and good water resistance. Development is desired.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to a film for oxygen absorber and a package for oxygen absorber, which comprises a silicone resin, a polyolefin-silicone copolymer, and a thermoplastic resin composition containing polyolefin or polyamide as a constituent. .

Examples of the silicone resin used in the present invention include crosslinked organopolysiloxanes such as dimethylpolysiloxane and methylvinylpolysiloxane.
The polyolefin-silicone copolymer includes, for example, block copolymers, graft copolymers and crosslinked products of polyolefin and the above-mentioned organopolysiloxane, which may be used alone or in combination. Examples of the polyolefin include low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), polypropylene (PP), poly-4-methylpentene-1 (TPX), or ethylene with acrylic acid, methyl acrylate, and acrylic. Ethyl acid, methacrylic acid, methyl methacrylate, vinyl acetate,
Examples thereof include butene, pentene, hexene, heptene, octene, and an ethylene copolymer composed of 4-methylpentene-1.

As the third component polyolefin,
For example, LDPE, LLDPE, PP, TPX or ethylene and acrylic acid, methyl acrylate, ethyl acrylate, methacrylic acid, methyl methacrylate, vinyl acetate, butene, pentene, hexene, heptene, octene, or 4-methylpentene- And an ethylene-based copolymer consisting of 1 and the like. Examples of polyamides include 6-nylon, 6,6-nylon and 11-nylon.

An example of the thermoplastic resin composition used in the present invention is, for example, Silgraf ^™ (silicone content 50
%) (Manufactured by Nippon Unicar Co., Ltd.), but those having a silicone content of 45% (W / W) or less are preferable, more preferably 10-40% (W / W), and further preferably 15 It is about -35% (W / W).

This Sylgraft ^™ is blended with polyolefin or polyamide to give a silicone content of about 45% (W /
W) and below resins have good spreadability, and are preferable as the thermoplastic resin used in the present invention. As the polyolefin or polyamide to be blended, any of the above can be used, but when, for example, Silgraft ^™ is produced using LLDPE, polyolefin or polyamide such as LLDPE, PP, TPX, for example, nylon 6, or Nylon 66 or the like is preferably mixed in a proportion of about 8-3 parts by weight of polyolefin or polyamide with respect to 3-8 parts by weight of sylgraft.

Further, the thermoplastic resin composition used in the present invention is subjected to a mechanochemical reaction, that is, a polyolefin and a reactive organopolysiloxane are kneaded by heating, and, if desired, after the completion of the mechanochemical reaction, a polyolefin of the same or different type is further added. Alternatively, it is also produced by adding and kneading polyamide. Further, the thermoplastic resin composition can be obtained by uniformly heating and mixing the above silicone resin, polyolefin, silicone copolymer and polyolefin or polyamide, and also by the method disclosed in JP-A-3-140345.

The above thermoplastic resin composition used in the present invention
The material is formed into a film by a conventional method, for example, an inflation method.
Method and T-die method. The thickness of the film
Is about 5-100 μm, preferably 10-90 μm, and
It is preferably about 15-80 μm. The silicone
Develop a thermoplastic resin composition containing less than 45% (W / W)
The film produced by rolling is new and contains
Good gas permeability, demand for gas permeability such as oxygen scavenger
It is suitable for the package. In particular, the film thickness is 100 μm or less,
Preferably 90 μm-10 μm, more preferably 80 μm
Oxygen permeability (cm)³/ M²24 hours
atm) is 1 × 10^FiveOr more, preferably 1 × 10 ⁶that's all
Are particularly preferred.

The oxygen scavenger package of the present invention is obtained by packaging the above-mentioned film alone or a laminated sheet having the film as the uppermost layer, and then packaging the oxygen scavenger with the film as the outermost layer by a conventional method. You can The laminated sheet is preferably a 2-4 layer sheet with a breathable sheet such as paper, non-woven fabric, split cloth and perforated resin film. When used for such a laminated sheet, P should be added to the sylgraft (trade name).
It is particularly preferable that P, TPX or nylon 6 or nylon 66 is blended to form a thermoplastic resin having a silicone content of about 40 to 10% and a film thickness of about 15 to 80 μm. The oxygen absorber is, for example, sulfite, bisulfite,
Thiosulfate, dithionite, hydroquinone, catechol, resorcin, pyrogallol, gallic acid, rongalit, ascorbic acid, ascorbate, isoascorbic acid, isoascorbate, sorbose, glucose, lignin, dibutylhydroxytoluene, butyl Hydroxyanisole, ferrous salt, iron powder, etc.
Further, these components may be used in combination with a carbon dioxide gas generating agent and a carbon dioxide gas absorbing agent, and the deoxidizing agent may be packaged in a breathable sheet such as the above paper.

Various shapes can be adopted for the package of the present invention, and typical ones are shown in FIGS.
1 to 2, the uppermost layer A represents the uppermost layer of the uppermost sheet of the multilayer structure sheet provided on a part (one surface) of the package, usually 5 to 100 μm, and more preferably 10 to 8 μm.
It is composed of a film of the invention having a thickness of 0 μm. Next, the middle layer B preferably has a Gurley type air permeability of 1000 sec / 100.
Although it is convenient to use paper of ml or less, a nonwoven fabric made of plastic or a microporous membrane made of plastic may be used. That is, as the paper, Japanese paper, Western paper, synthetic paper, plastic mixed paper, etc., and as the non-woven fabric, plastic fibers exemplified by polyethylene, polypropylene, polyester, nylon, etc. are joined in a sheet shape by heat, pressure, adhesive, etc. Things can be used.

Specific examples thereof include Tyvek (Dupont, USA) Preslon (Nitto Denko Corp.), Spunbond (Asahi Kasei Corp.) and the like. Alternatively, a perforated plastic film may be used. Further, as the microporous film, a cold-stretched film of polyethylene or polypropylene resin,
Those obtained by a method such as stretching a foreign matter-containing film or irradiating an electron beam can be used. Specific examples thereof include Hypore (Asahi Kasei Co., Ltd.), Microtex (Nitto Denko Corporation), NF Sheet (Tokuyama Soda Co., Ltd.) and the like. It is preferable to provide the lower layer C when the middle layer B does not have the above-mentioned paper or the heat-sealing function or a non-woven fabric of a plastic or a microporous film having a poor heat-sealing function is used.

The lower layer C usually has a softening point lower than that of the plastic constituting the middle layer B and has a Gurley air permeability of 100.
It is composed of a perforated plastic film capable of heat sealing of 0 seconds / 100 ml or less, a non-woven fabric or a microporous plastic film. Specific examples of the perforated plastic film include a film made of a material such as polyethylene, polypropylene, polyethylene vinyl acetate copolymer, or polyethylene ionomer. As a method for adjusting the sheet by stacking these uppermost layers, middle layers or lower layers,
A dry method, a wet laminating method, an extrusion laminating method, or the like, which is commonly used when preparing a laminate, is used. The package of the present invention is obtained by stacking the uppermost layer A, the middle layer B, and the lower layer C in the order AB or ABCC to obtain a sheet, and stacking two sheets on each other to seal the four sides. The obtained sheet may be folded in two and sealed on three sides.

[0015]

EXAMPLES The present invention will be described in more detail below with reference to examples. Example 1 60 parts of Sylgraft ^™ 250 and 40 parts of nylon 66 or polypropylene were heat-melted to obtain a film of the present invention by an inflation method.

The oxygen permeability of the film obtained by this method was measured according to the ASTM D1434 method. The results are shown in Table 1.

[Table 1] * Nippon Unicar Co., Ltd .: Mechanochemical resin of LLDPE and organopolysiloxane, silicone content 5
0% ** The average value of n = 2

Example 2 A polypropylene-based non-woven fabric was printed with characters and manufactured in the same manner as in Example 1 to obtain a film having the formulation shown in Table 2 below (thickness: 3).
0 μm to 40 μm) was laminated on the printed surface, and a perforated polyethylene sheet was laminated on the non-printed surface of the nonwoven fabric to obtain a packaging material of the present invention having a three-layer structure. The content of the iron-based oxygen scavenger Modran S (manufactured by Nippon Kayaku Co., Ltd.) was put into the inside of the obtained packaging material with the film surface of the formulation shown in Table 2 below as the outside, and three-sided sealing was performed according to the present invention. A package was obtained.

The oxygen absorber package produced by this method was packaged in a nylon laminar bag in a volume of 500 ml. 25 ° C, humidity 10
The results of measuring the oxygen concentration in the outer bag with an oxygen meter (manufactured by Toray) at 0% are shown in Table 2 below.

[Table 2] Blended resin film Oxygen concentration ^** Sylgraft 250 Nylon (6) 24h 48h 72h (%) (%) 40 60 6.6 4.0 1.7 50 50 4.4 0.9 0.02 60 40 0.4 0.008 0 100 0 9.5 4.5 2.2 ^** Data The average value of n = 5; the ratio of 60% silgraft was 0.1% or less within 48 hours, and the practicability was considerably high. No bleeding of the contents (oxygen scavenger) was observed at all.

[0019]

As is clear from Table 1, the film of the present invention has a very good oxygen permeability and is also excellent in water resistance and suitable as a packaging material for an oxygen scavenger. According to the results shown in Table 2, the oxygen scavenger package of the present invention has excellent oxygen absorption capacity, high transparency, and back printing, and the printing ink does not come into direct contact with foods. There is no oozing out. Therefore, it is safe and extremely useful when used in foods.

[Brief description of drawings]

FIG. 1 is an example of a package of the present invention.

FIG. 2 is another example of the package of the present invention.

[Explanation of symbols]

 A Uppermost layer (special film of the present invention) B Middle layer (paper, nonwoven fabric, etc.) C Lower layer (perforated film, nonwoven fabric, etc.) D Contents (oxygen scavenger)

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Sadaichi Matsumoto 166 Fukachocho, Matsuzaka City, Mie Prefecture (72) Inventor Kiyomichi Iwasa 1-105 Shiratsukacho, Tsu City, Mie Prefecture

Claims (3)

[Claims] 1. A silicone resin, a polyolefin,
A film for an oxygen scavenger comprising a thermoplastic resin composition containing a silicone copolymer and a polyolefin or a polyamide as constituent components. 2. Silicone resin, polyolefin
A film comprising a thermoplastic resin composition containing a silicone copolymer and a polyolefin or polyamide as constituent components and having a silicone content of 45% or less. 3. Silicone resin, polyolefin
An oxygen absorber package packaged with a film comprising a thermoplastic resin composition containing a silicone copolymer and a polyolefin or a polyamide as constituent components.