JP4573013B2 - Oxygen absorber outer packaging - Google Patents

Description

【００３０】
比較例１
実施例１において、ＫＯＮ／接着性樹脂／ＮＹに代えて、ＫＯＮのみを用いて押し出しラミネーション法により接着した以外は、全く同様にして多層フイルムを作成し、水蒸気透過度、酸素透過度、突き刺し強度（耐ピンホール性）を測定した。その結果を表１に示した。
次に、得られた多層フイルムを用いて、落下試験を行った。落下試験後の脱酸素剤外装包装体は、10サンプル中、２サンプルの多層フイルムにピンホールの発生が認められた。
【００３１】
実施例２
実施例１において、（Ａ）層として厚さ１５μｍのポリ塩化ビニリデンコートした二軸延伸ポリアミド（ＫＯＮ）（東洋紡（株）製、商品名Ｎ−８１２ＡＥ）を用い、（Ｂ）層として厚さ１０μｍのナイロン６（ＮＹ）を有するＬＬＤＰＥ／ＮＹ／ＬＬＤＰＥ＝１０／１０／１０μｍの複合フィルム（グンゼ（株）製、商品名ＮＹ＃３０Ｂ）を用い、（Ｃ）シーラント樹脂層として厚さ２０μｍの線形低密度ポリエチレン（ＬＬＤＰＥ）（東セロ（株）製、商品名ＴＵＸ−ＦＣＤ）を用い、（Ｂ）層と（Ｃ）層の層間をウレタン系接着剤（武田薬品（株）製、商品名Ａ５１５／Ａ１２）を厚さ約３μｍにて用いてドライラミネートした以外は全く同様にして３種４層フイルムを作成し、水蒸気透過度、酸素透過度、突き刺し強度（耐ピンホール性）を測定した。その結果を表１に示した。
【００３２】
表１の結果から、（Ｂ）ＮＹ層と（Ｃ）シーラント樹脂層との層間をドライラミネーションする方法でも、水蒸気バリヤー性、酸素バリヤー性を維持しながら、同時に、実用的な耐ピンホール性に向上、改善できることが分かる。
次に、得られた多層フイルムを用いて、落下試験を行った。落下試験後の脱酸素剤外装包装体には、破損やピンホールの発生が認められたものは無かった。
【００３３】
実施例３
実施例１において、（Ｂ）ポリアミド層としてナイロン６（三菱化学（株）製、商品名ノバミッド１０２２）とＭＸＤ６（三菱瓦斯化学（株）製、商品名ＭＸナイロン６５６０）を重量比80:20にて混合した樹脂フィルムを温度85℃、倍率3.0で延伸してなる２０μｍの積層フィルムを用い、（Ａ）層と（Ｂ）層、（Ｂ）層と（Ｃ）層の各層間をドライラミネーションで接着した以外は、全く同様にして３種３層フイルムを作成し、水蒸気透過度、酸素透過度、突き刺し強度（耐ピンホール性）を測定した。その結果を表１に示した。
【００３４】
表１の結果から、ＫＯＮ／ＮＹ／ＬＬＤＰＥの各層間をドライラミネーション法によって貼り合せても、水蒸気バリヤー性、酸素バリヤー性を保持しながら、同時に、実用的な耐ピンホール性に向上、改善できることが分かる。
次に、得られた多層フイルムを用いて、落下試験を行った。落下試験後の脱酸素剤外装包装体には、破損やピンホールの発生はなかった。
【００３５】
【発明の効果】
本発明によって、水蒸気バリヤー性、酸素バリヤー性を保持し、同時に、突き刺し強度（耐ピンホール性）を十分実用的なレベルまでに向上、改善でき、安心して物流過程に供することができる脱酸素剤外装包装体が実現できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an oxygen scavenger outer packaging body that contains an oxygen scavenger.
[0002]
[Prior art]
In recent years, the use of oxygen scavengers has become established as a convenient and reliable storage method for foods, pharmaceuticals, cosmetics and other oxidizable items, mold and other microbial contamination, and items susceptible to spoilage. Oxygen scavengers in the form of films and the like have been industrially produced. These oxygen scavengers collect a certain amount of sachet-shaped oxygen scavengers, or cut sheets of oxygen scavengers such as sheets or films into a certain length, or a series of sachet oxygen scavengers. Each bobbin obtained by winding a certain amount of body (web) is wrapped with an oxygen barrier film and stored and used in a physical distribution process.
[0003]
Conventionally, as an oxygen barrier container for storing an oxygen scavenger, a stretched polyamide (KON) / polyethylene (PE) coated with polyvinylidene chloride (hereinafter, for example, a multilayer film laminated in the order of a KON layer and a PE layer) KON / PE) has been used.
[0004]
However, in recent years, as KON / PE exterior packaging bodies that have been used conventionally have poor physical handling strength, as packaging bodies containing oxygen scavengers are manufactured in large quantities and the logistics process of product transportation becomes complicated and intense. It is sufficient, and pinholes may be generated in the multilayer film during the transportation distribution process, and the oxygen scavenger may be deactivated by the invading oxygen.
In order to be able to handle practically, sufficient pinhole resistance is required, and the piercing strength is required to be 12N or more.
[0005]
On the other hand, as a packaging material having excellent gas barrier properties, a layer type configuration including an ethylene-vinyl acetate copolymer saponified product (EVOH) resin layer and a polyamide resin layer made of a blend of crystalline polyamide MXD6 and another polyamide is used. JP-A-4-2105050 discloses a heat seal layer / biaxially stretched EVOH layer / polypropylene, polyamide or polyester biaxially stretched film layer in JP-A-53-35778, respectively.
[0006]
However, the saponified ethylene-vinyl acetate copolymer layer (EVOH), which is the base material of the intermediate layer, has a weak water vapor barrier property and is insufficient as a container for storing and distributing oxygen scavengers.
[0007]
[Problems to be solved by the invention]
In the oxygen barrier film for packaging the oxygen scavenger, (1) the oxygen scavenger may contain water that is a catalyst for expressing oxygen absorption activity, so that water does not volatilize outside the container. In addition, it has a high water vapor barrier property, and (2) in general, since it is stored and stored in a depressurized state by a degassing operation, etc., it has high strength and pinhole resistance, and (3) it can withstand severe handling in logistics processes. 4) sufficient strength and pinhole resistance, and (4) good operability at the time of sealing or opening.
[0008]
The object of the present invention is to solve the above-mentioned problems of the prior art in the storage and distribution of oxygen scavengers, have a good balance of oxygen barrier properties, water vapor barrier properties and pinhole resistance, and satisfy functional requirements. It is in providing an oxygen agent exterior packaging body.
[0009]
[Means for Solving the Problems]
As a result of studying a method for solving the above problems, the present inventor uses a laminated film comprising (A) a polyvinylidene chloride-coated stretched polyamide resin layer, (B) a polyamide resin layer, and (C) a sealant resin layer. As a result, the inventors have found that the object can be achieved, and have completed the present invention.
[0010]
That is, the present invention is an oxygen scavenger outer package comprising an oxygen barrier film containing an oxygen scavenger, wherein the oxygen barrier film comprises (A) a polyvinylidene chloride-coated stretched polyamide resin layer, An oxygen-absorbing agent outer package characterized by being a multilayer film comprising (B) a polyamide resin layer and (C) a sealant resin layer.
With this configuration, KON / PE retains the excellent water vapor barrier and oxygen barrier properties, improves pinhole resistance to a practical level, stores oxygen scavengers safely, and can be used in logistics processes. An outer packaging that can be provided is provided.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, a multilayer film comprising (A) a polyvinylidene chloride-coated stretched polyamide resin layer, (B) a polyamide resin layer, and (C) a sealant resin layer is used.
[0012]
The (A) polyvinylidene chloride-coated stretched polyamide resin (KON) layer used in the present invention is a surface of a stretched amorphous polyamide resin or a mixture of an amorphous polyamide resin and another polyamide resin. It is a coated resin layer.
Amorphous polyamide can be obtained by pressure melt polymerization, decarboxylation condensation reaction, etc. using dicarboxylic acid, diamine, lactam, diisocyanate and the like as raw materials. Here, examples of the dicarboxylic acid include adipic acid, suberic acid, azelaic acid, terephthalic acid, and isophthalic acid. Examples of the diamine include hexamethylene diamine, trimethyl hexamethylene diamine, isophorone diamine, bis-p- (aminocyclohexyl) methane, and bis-p- (aminocyclohexyl) ethane. Examples of the lactam include caprolactam and laurocaprolactam. As the diisocyanate, for example, diphenyl methane diisocyanate, tolylene diisocyanate and the like are used. Specifically, nylon 6, nylon 12, nylon 11, nylon 6-6, nylon 6-10, nylon 6-12, or a copolymer or a mixture thereof is used.
(A) Polyvinylidene chloride-coated stretched polyamide resin is stretched under stretching conditions that exhibit a stretching effect, for example, stretched at a stretch temperature of 50 to 150 ° C. under a stretch ratio of 2 to 6 times, and then coated with polyvinylidene chloride and dried. KON is obtained.
[0013]
(B) The polyamide resin (NY) layer is a layer made of stretched polyamide resin or unstretched polyamide resin. The polyamide resin includes an amorphous polyamide or a polyamide composition of an amorphous polyamide and another polyamide.
Amorphous polyamide can be obtained by pressure melt polymerization, decarboxylation condensation reaction, etc. using dicarboxylic acid, diamine, lactam, diisocyanate and the like as raw materials. Here, examples of the dicarboxylic acid include adipic acid, suberic acid, azelaic acid, terephthalic acid, and isophthalic acid. Examples of the diamine include hexamethylene diamine, trimethyl hexamethylene diamine, isophorone diamine, bis-p- (aminocyclohexyl) methane, and bis-p- (aminocyclohexyl) ethane. Examples of the lactam include caprolactam and laurocaprolactam. As the diisocyanate, for example, diphenyl methane diisocyanate, tolylene diisocyanate and the like are used.
[0014]
Specifically, nylon 6, nylon 12, nylon 11, nylon 6-6, nylon 6-10, nylon 6-12, or a copolymer or a mixture thereof is used.
Furthermore, other polyamides mixed with the amorphous polyamide can be obtained by polycondensation reaction of ω-aminocarboxylic acid, polycondensation reaction of dibasic acid and dicarboxylic acid, etc. A mixture of crystalline polyamide MXD6 obtained by polycondensation with adipic acid and other polyamides may be used. The mixing weight ratio of the amorphous polyamide and the crystalline polyamide is 100/0 to 20/80.
(B) The polyamide resin is preferably a stretched polyamide that has been biaxially stretched under stretching conditions that exhibit a stretching effect, for example, a stretching temperature of 50 to 150 ° C. and a stretching ratio of 2 to 6 times.
[0015]
The sealant resin layer (C) used in the present invention is made of polyethylene (PE) such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), polypropylene (PP ) -Based olefin resins, ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate copolymer (EMA) ), Ethylene-ethyl acrylate-maleic anhydride copolymer (E-EA-MAH), ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMMA), ionomer (ION), etc. Examples thereof include ethylene copolymer resins. Among these, olefin resins such as LDPE and LLDPE are more preferably used.
[0016]
The layers (A), (B), and (C) can be laminated by an extrusion lamination method in which an adhesive resin (Ad) is used and extruded between the layers.
[0017]
The adhesive resin (Ad) used in that case is polyethylene (PE) such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), Olefin resins such as polypropylene (PP), ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate-maleic anhydride copolymer (E-EA-MAH), ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMMA), ionomer (ION) Other examples include ethylene copolymer resins such as Reolefinic resin such as ethylene-vinyl acetate copolymer or ethylene elastomer, monobasic unsaturated fatty acid such as acrylic acid or methacrylic acid, or dibasic such as maleic acid, fumaric acid or itaconic acid The thing which couple | bonded the anhydride of the fatty acid chemically is illustrated.
[0018]
The outer package of the present invention is a multilayer film package having a thickness of 250 μm or less containing an oxygen scavenger.
The thickness of the layer (A) is preferably in the range of 10 to 30 μm from the viewpoint of functionality, handleability and cost. (B) The thickness of the layer is preferably in the range of 15 to 30 μm in terms of functionality and price.
(C) The thickness of the layer is preferably in the range of 20 to 50 μm. If the thickness is 20 μm or less, the sealing strength is lowered and there is a concern about breakage during use. If the thickness is 50 μm or more, the cost is increased, and the total thickness of the film is increased and the handling property is lowered. Moreover, when using the adhesive resin layer (Ad) which adhere | attaches each of these each layer, the range of 10-25 micrometers is preferable at the point of workability | operativity, economical efficiency, and handleability.
[0019]
For example, in the case of a three-layer five-layer film of (A) / (Ad) / (B) / (Ad) / (C), first, (A) KON film (B) While feeding the NY film by a roll, the adhesive resin layer (Ad) is melt-extruded and laminated and adhered between the rolls, and then the adhesive resin layer (B) between the NY film surface and the (C) sealant layer ( Ad) is extruded, laminated, and adhered to obtain a multilayer package of the above three types and five layers.
[0020]
Here, a film composed of the number of base film types (n) and the number of adhesive resin layers (m) is expressed as an n-type m-layer film. The adhesive resin layer is a layer having a thickness of 5 μm or more and 250 μm or less. Layers having a thickness of less than 5 μm, such as dry lamination adhesives and coating agents, are not included.
[0021]
In the outer package of the present invention, each layer of (A) KON, (B) NY, and (C) sealant, which are constituent elements, is manufactured individually for each layer, and then the layers are separated according to a predetermined combination and order. The exterior packaging body is manufactured by pasting. At that time, the adhesive (laminate) method is an extrusion lamination method in which an adhesive resin layer (Ad) is extruded or laminated between all or a part of each layer, and an adhesive is applied to each layer or part, and pressure bonding is performed. And a dry laminating method for drying. Specifically, as a lamination method between the A / B layers, (A) between the KON resin layer and (B) NY resin layer, or (B) between the NY resin layer and (C) the sealant layer, The extrusion lamination method in which the adhesive resin layer (Ad) is inserted is more preferable in terms of adhesiveness and flexibility than the dry lamination method in which the adhesive is thinly applied (usually several μm or less).
[0022]
The outer package obtained by the present invention has a water vapor permeability of 25 ° C., 0 → 75% RH, 1.0 g / m ² · 24 hr or less, an oxygen permeability of 25 ° C., 60% RH, 20 ml / m ² · It has characteristics of 24 hr · atm or less and a piercing strength of 12 N / pen nib radius 0.5 mm and 50 mm / min or more. As a result of investigation by the present inventor, it was found that pinhole occurrence accidents drastically decrease at a puncture strength of 10N. In view of the safety factor, if the piercing strength is 12 N or more, it can be determined that the pinhole resistance is practical in handling.
[0023]
The oxygen scavenger to be packaged is an oxygen-absorbing substance exemplified by iron or ascorbic acid, which is packaged with a breathable packaging material or blended with a thermoplastic resin. It is an oxygen scavenger in any form such as a shape. Specifically, accumulation of sachet-shaped oxygen scavengers, bobbins wound with a continuous package (web) of sachet-shaped oxygen scavengers, or bundles or rolls of sheet-like or film-like oxygen scavengers. .
[0024]
The exterior packaging body of the present invention is a packaging body that is used for the storage and distribution process of the produced oxygen scavenger, and can be widely used as packaging bodies for other food and beverage bottles and barrels. The outer package is usually combined with the sealant layers and sealed by various heat-sealing methods such as heat bar sealing, impulse sealing, and high frequency sealing to obtain a bag-shaped storage body. Then, a certain amount of the oxygen scavenger produced therein is accommodated, vacuum operation or deaeration operation is performed as desired, hermetically sealed, and stored and distributed.
[0025]
【Example】
Hereinafter, the present invention will be described in detail by way of examples. The physical properties of the multilayer film or oxygen scavenger package obtained in the examples were measured by the following method.
(1) Water vapor permeability Unit: g / m ² · 24 hr
The obtained multilayer film was measured according to JIS-Z-0208.
Oxygen permeability Unit: ml / m ² · 24 hr
The obtained multilayer film was measured with an oxygen permeability measuring device (OXY-TRAN100 type, manufactured by Modern Control Co., Ltd.) at 25 ° C. and 60% RH.
[0026]
(3) Puncture strength (pinhole resistance) Unit: N (Newton) / Pin tip radius 0.5 mm, 50 mm / min
The obtained multilayer film was pierced with a pin having a diameter of 1 mm and a tip curvature radius of 0.5 mm under a speed condition of 50 mm / min, and the load (N) at the time of opening was measured.
(4) Drop test sachet-shaped oxygen absorber package (Mitsubishi Gas Chemical Co., Ltd., trade name AGELESS Z-23PTR) 3,000 continuous rolls (web) spirally wound around a bobbin Is sealed by the heat seal method while performing decompression operation using the obtained multilayer film, 10 samples of the oxygen scavenger outer packaging are obtained, and these oxygen scavenger outer packagings are placed on the concrete floor from a height of 2 m. The film was allowed to fall 10 times repeatedly, and then the multilayer film was observed for damage and pinholes.
[0027]
Example 1
15 μm thick biaxially stretched nylon (KON) (trade name N-812AE) film and 15 μm thick biaxially stretched polyamide (NY) (manufactured by Toyobo Co., Ltd.) coated with polyvinylidene chloride on one side , Trade name N-812AE) While sending out the film with a hot roll so that the polyamide surface is opposed, 300 low-density polyethylene adhesive resin (Ad) (trade name: Misolan 11P, manufactured by Mitsui Chemicals, Inc.) A laminated film of KON / adhesive resin layer / ON = 15/15/15 μm was obtained by melting and extruding at ° C. Next, in the same manner, while the NY side of the obtained film and a linear low density polyethylene-based (product name: TUX-FCD, manufactured by Tosero Co., Ltd.) film as a sealant resin are opposed to each other by a hot roll, The PE adhesive resin layer (Ad) is melt-extruded, bonded, and finally, KON / Ad / NY / Ad / LLDPE = 3 / 5-layer film of 15/15/15/15/30 μm (total thickness 90 μm) Got. The obtained multilayer film was measured for water vapor permeability, oxygen permeability, and puncture strength (pinhole resistance) by the above methods. The results are shown in Table 1. Each measurement was performed 10 times to indicate the numerical range.
[0028]
From Table 1, it was found that pinhole resistance can be greatly improved and improved to 12N or more, which is a reference value that can be practically handled, while maintaining water vapor barrier property and oxygen barrier property.
Next, a drop test was performed using the obtained three kinds of five-layer films. The oxygen scavenger package after the drop test did not break or generate pinholes. Further, the adhesive resin layer (Ad) between the (A) layer and the (B) layer improved the adhesive property like a cushion, and had high flexibility and handleability (handling property).
[0029]
[Table 1]

[0030]
Comparative Example 1
In Example 1, a multilayer film was prepared in the same manner except that only KON was used instead of KON / adhesive resin / NY and adhesion was performed by the extrusion lamination method, and water vapor transmission rate, oxygen transmission rate, and piercing strength were produced. (Pinhole resistance) was measured. The results are shown in Table 1.
Next, a drop test was performed using the obtained multilayer film. In the oxygen scavenger packaging after the drop test, generation of pinholes was observed in 2 samples of 10 samples.
[0031]
Example 2
In Example 1, (A) a 15 μm-thick polyvinylidene chloride-coated biaxially stretched polyamide (KON) (trade name N-812AE, manufactured by Toyobo Co., Ltd.) was used as the (A) layer, and a (B) layer was 10 μm thick. Using a composite film of LLDPE / NY / LLDPE = 10/10/10 μm (trade name NY # 30B, manufactured by Gunze Co., Ltd.) having a nylon 6 (NY) of (C) a linear shape having a thickness of 20 μm as a sealant resin layer Using low-density polyethylene (LLDPE) (trade name TUX-FCD, manufactured by Tosero Co., Ltd.), the layer between the (B) layer and the (C) layer is a urethane adhesive (manufactured by Takeda Pharmaceutical Co., Ltd., trade name A515 / Three types of four-layer films were prepared in the same manner except that A12) was dry laminated using a thickness of about 3 μm, and water vapor permeability, oxygen permeability, piercing strength (pinhole resistance) ) Was measured. The results are shown in Table 1.
[0032]
From the results shown in Table 1, the method of dry lamination between the (B) NY layer and the (C) sealant resin layer also maintains practical water resistance and oxygen barrier properties, while at the same time providing practical pinhole resistance. It can be seen that it can be improved.
Next, a drop test was performed using the obtained multilayer film. None of the oxygen scavenger outer packagings after the drop test showed any damage or pinholes.
[0033]
Example 3
In Example 1, (B) Nylon 6 (Mitsubishi Chemical Co., Ltd., trade name Novamid 1022) and MXD6 (Mitsubishi Gas Chemical Co., Ltd., trade name MX Nylon 6560) are used as a polyamide layer in a weight ratio of 80:20. Using a 20 μm laminated film obtained by stretching the mixed resin film at a temperature of 85 ° C. and a magnification of 3.0, the layers (A) and (B), and (B) and (C) are dry laminated. Except for bonding, a three-layer three-layer film was prepared in the same manner, and the water vapor permeability, oxygen permeability, and piercing strength (pinhole resistance) were measured. The results are shown in Table 1.
[0034]
From the results in Table 1, even if each layer of KON / NY / LLDPE is bonded by the dry lamination method, it is possible to improve and improve the practical pinhole resistance while maintaining the water vapor barrier property and oxygen barrier property. I understand.
Next, a drop test was performed using the obtained multilayer film. The oxygen scavenger package after the drop test did not break or generate pinholes.
[0035]
【The invention's effect】
According to the present invention, an oxygen scavenger that can maintain a water vapor barrier property and an oxygen barrier property, and at the same time, can improve and improve the puncture strength (pinhole resistance) to a sufficiently practical level, and can be safely used in a physical distribution process. An outer package can be realized.

Claims (4)

An oxygen scavenger outer package comprising an oxygen barrier film containing an oxygen scavenger, wherein the oxygen barrier film comprises (A) a polyvinylidene chloride-coated stretched polyamide resin layer, and (B) a polyamide resin layer. , and I (C) multi-layer film der consisting sealant resin layer, further wherein the oxygen barrier film is water vapor transmission rate is ^{1.0g / m 2 · 24hr (25} ℃, 0 → 75% RH) or less, and, the oxygen permeability of ^{20ml / m 2 · 24hr · atm} (25 ℃, 60% RH) or less, and, piercing strength and characteristics 12N / ballpoint destination radius 0.5 mm, the der Rukoto than 50 mm / min Oxygen scavenger outer packaging. The oxygen barrier film is a multilayer film in which (A) resin layer and (B) resin layer, or (B) resin layer and (C) resin layer are laminated with (Ad) adhesive polyolefin resin layer. The outer packaging body according to claim 1. The oxygen barrier film is a multilayer film in which (A) a resin layer and (B) a resin layer, or (B) a resin layer and (C) a resin layer are laminated by a dry lamination method. Exterior packaging. The exterior according to claim 1, wherein the oxygen barrier film has (A) a resin layer thickness of 10 to 30 µm, (B) a resin layer thickness of 15 to 30 µm, and (C) a resin layer of 20 to 60 µm. Packaging body.