【発明の詳細な説明】[Detailed description of the invention]
本発明は容器に密閉収納して物品を保存する
際、当該物品が空気中の酸素により酸化された
り、好気的微生物の増殖により腐敗したりするの
を防ぐために、植物種子または植物の葉茎を同封
封入し、物品を保存する方法に関する。
従来、保存せんとする物品を収納した容器内の
酸素を減少もしくは除去して保存性を高めんとす
る試みは数多くある。物理的方法では真空包装、
ガス置換包装即ち炭酸ガス、窒素ガス充填包装等
がこれに当るが近年、急速に普及されてきた方法
は通常「脱酸素剤」と呼ばれる化学的方法であ
る。「脱酸素剤」と呼ばれるものの内容は主とし
て酸素吸収反応系によるもの被酸化速度の早
い物質（還元剤）を利用するもの、に大別出来
る。
に属するものとしてはグルコース−グルコー
スオキシダーゼ系、グルコース−アルカリ溶液
等、に属するものとしてはアスコルビン酸、イ
ソアスコルビン酸及びそのアルカリ塩、亜硫酸、
チオ硫酸、次亜硫酸のアルカリ塩、鉄、マンガン
或いはその塩類、ピロガロール、ロンガリツト、
亜二チオン酸塩等に場合によつてアルカリ塩を配
合して主剤をなしている。これ等脱酸素剤はそれ
ぞれに容器中の酸素を除去する能力があるが、化
学反応であるために反応のコントロールがきかな
い。即ち脱酸素剤が酸素に曝露され、酸素吸収能
力の100％が費やされればも早脱酸素剤の機能は
果たさない。従つて容器の開閉回数に制限があ
る。又、容器自体の材質が酸素に対して高いバリ
ヤー性がなければ短時間で機能は停止する。
本発明は上述したような化学反応の脱酸素剤の
限界を打ち破るべく新しい見地からの容器内酸素
除去方法を思考し、種々研究の結果生物呼吸の利
用に着目するに至つた。生物呼吸とは言うまでも
なく、生物が酸素をとり入れ、炭酸ガスを排出す
る生理作用である。呼吸作用も生化学反応には違
いないが脱酸素剤に於ける化学反応と相異し、生
物体が生きている間継続する作用であるから、あ
る条件下に生物体を置けば酸素を除去する機能は
上記化学反応に比べ遥かに長期間脱酸素能力を保
持する筈であり、又排出する炭酸ガスは前述した
ガス置換にも似た効果を発揮するものと考えた。
又容器の材質の酸素ガスバリヤー性が化学的脱酸
素剤程厳密でなくても封入した生物体の呼吸量が
それを上回つて大きければ目的は達せられると考
えた。多くの実験を重ねた結果これらの仮説は実
証され、本発明者らはこゝに植物種子または植物
の葉茎による脱酸素法による物品保存方法を完成
した。
本発明の方法を適用し得る保存物品とてして
は、容器中の酸素を減少もしくは除去せしめるこ
とにより、当該物品の酸化或いは微生物の増殖を
抑制し得るもの全てに適用できるが、例えば微生
物増殖抑制対象としてパン、菓子、モチ、穀類、
練製品、珍味、畜肉魚介類、惣菜類、香辛料類、
皮革製品、竹製品等があげられ、酸化抑制対象と
して油脂、油菓、油揚食品、肉類、金属製品等が
あげられる。これらを合成樹脂製或いは金属箔製
フイルムで袋状にパツク包装したもの或いはビン
詰、カン入り等の包装形態に適用するのが好適で
ある。
次に実施例により本発明の方法をさらに詳細に
説明する。植物種子として籾、そばの種子、植物
の葉茎としてはツゲ、マサキ、マキ、ヒイラギ、
シダの葉茎を用い、保存する物品としては食パ
ン、餅を採用した。そして封入する容器は酸素ガ
スバリヤー性の高いナイロン−ポリエチレンラミ
ネート袋（ユニチカ(株)製、25℃湿度50％以下で24
時間に１m2当り酸素ガス透過15c.c.以下、グンゼ(株)
製、25℃湿度50％以下で24時間に１m2当り酸素ガ
ス透過35c.c.以下）と酸素バリヤー性の低いポリエ
チレン袋（クレハ(株)製、0.02mm、25℃湿度50％以
下で24時間に１m2当り酸素ガス透過2500c.c.）を使
用したが本発明はこれによつて限定されるもので
はない。なお、植物種子については休眠状態を打
破するために、エチレン処理を施したものを使用
した。パン、餅を用いた微生物増殖抑制実験は25
℃の恒温器内で実施し、主としてカビ集落の発生
の有無をもつて指標とした。又、呼吸量は容器内
に酸素センター（三菱互斯化学(株)製、商品名エー
ジレスアイ、酸素濃度0.5％以上で青、0.1％以下
で赤）を入れて観察すると共に容器内の炭酸ガス
濃度を測定（ガステツク）した。
実施例 １
そば種子５ｇを10cm×10cmの予め含水させた不
織布（パルクロス102−本州製紙）に包み５ケ作
製した。25cm×32cmのナイロン−ポリエチレンラ
ミネート袋に７cm×５cm×1.6cmの切餅２枚とそ
ば種子包装物１ケを入れ内容積を約200mlにした
後、袋の口をヒートシールで閉じ25℃の恒温器に
収納した。全く同じ資料を５ケ作製し内１ケを０
日目対照とした。又、そば種子包装物を収納しな
い同仕様の袋４ケを作り、対照として恒温器に入
れた。５日目毎に実験、対照それぞれ１ケ宛恒温
器から出し実験に供した。結果は次の通りであつ
た。
The present invention is designed to prevent plant seeds or plant leaves and stems from being oxidized by oxygen in the air or rotting due to the growth of aerobic microorganisms when storing items in a sealed container. Relates to a method for enclosing and preserving articles. In the past, there have been many attempts to reduce or remove oxygen in containers containing articles to be stored in order to increase their shelf life. Physical methods include vacuum packaging;
This includes gas displacement packaging, that is, packaging filled with carbon dioxide gas or nitrogen gas, and a chemical method that has become rapidly popular in recent years is usually a chemical method called "oxygen scavenger." The contents of the so-called "oxygen scavengers" can be broadly divided into those that mainly rely on oxygen absorption reaction systems and those that utilize substances that are rapidly oxidized (reducing agents). Those belonging to this category include glucose-glucose oxidase system, glucose-alkaline solution, etc., and those belonging to this category include ascorbic acid, isoascorbic acid and its alkali salts, sulfite,
Thiosulfuric acid, alkali salts of hyposulfite, iron, manganese or its salts, pyrogallol, rongarit,
The main ingredient is a dithionite salt, etc., mixed with an alkali salt depending on the case. Each of these oxygen scavengers has the ability to remove oxygen from the container, but since it is a chemical reaction, the reaction cannot be controlled. That is, even if the oxygen scavenger is exposed to oxygen and 100% of its oxygen absorption capacity is used up, it will not function as a quick oxygen scavenger. Therefore, there is a limit to the number of times the container can be opened and closed. Furthermore, if the material of the container itself does not have a high barrier property against oxygen, the container will stop functioning in a short period of time. In order to overcome the limitations of chemical reaction oxygen scavengers as described above, the present invention considered a new method for removing oxygen within a container from a new perspective, and as a result of various studies, focused on the use of biological respiration. Needless to say, biological respiration is a physiological process in which living organisms take in oxygen and expel carbon dioxide. Respiration is also a biochemical reaction, but it is different from the chemical reaction in oxygen scavengers, and it continues as long as an organism is alive, so if an organism is placed under certain conditions, oxygen can be removed. This function should maintain the deoxidizing ability for a much longer period of time than the chemical reaction described above, and the carbon dioxide gas discharged is thought to have an effect similar to the gas replacement described above.
We also thought that even if the oxygen gas barrier properties of the material of the container were not as strict as those of chemical oxygen scavengers, if the respiration rate of the enclosed organisms was greater than that, the objective could be achieved. As a result of many experiments, these hypotheses were verified, and the present inventors have now completed a method for preserving articles by deoxidizing them using plant seeds or leaves and stems. The method of the present invention can be applied to any preservation article that can be inhibited from oxidation or microbial growth by reducing or removing oxygen in the container. Bread, sweets, rice cakes, grains,
Pastified products, delicacies, meat and seafood, prepared dishes, spices,
Examples include leather products, bamboo products, etc., and targets for oxidation control include oils and fats, oil confections, fried foods, meat, metal products, etc. It is preferable to package these materials in a bag-like form using a synthetic resin or metal foil film, or to package them in bottles, cans, or the like. Next, the method of the present invention will be explained in more detail with reference to Examples. Plant seeds include paddy, buckwheat seeds, and plant leaves and stems include boxwood, masaki, maki, holly,
The leaves and stems of fern were used, and the items to be preserved were bread and rice cakes. The container to be sealed is a nylon-polyethylene laminate bag with high oxygen gas barrier properties (manufactured by Unitika Co., Ltd.;
Oxygen gas permeation per m2 per hour: 15 c.c. or less, Gunze Co., Ltd.
(manufactured by Kureha Co., Ltd., 0.02 mm, oxygen gas permeation of 35 c.c. or less per square meter per 24 hours at 25°C and humidity of 50% or less) and a polyethylene bag with low oxygen barrier properties (manufactured by Kureha Co., Ltd., 0.02 mm, 24°C at 25°C and humidity of 50% or less) Although an oxygen gas permeation rate of 2500 c.c. per m 2 per hour was used, the invention is not limited thereby. The plant seeds used were treated with ethylene in order to break the dormancy state. 25 microbial growth inhibition experiments using bread and rice cakes
The test was conducted in a constant temperature chamber at ℃, and the presence or absence of mold colonies was used as an indicator. In addition, the amount of respiration is measured by placing an oxygen center (manufactured by Mitsubishi Gosei Chemical Co., Ltd., trade name Ageless Eye, blue when the oxygen concentration is 0.5% or more, red when the oxygen concentration is 0.1% or less) in the container, and observing the carbon dioxide gas in the container. The concentration was measured (Gastec). Example 1 Five pieces of buckwheat seeds were prepared by wrapping 5 g of buckwheat seeds in a 10 cm x 10 cm pre-hydrated nonwoven fabric (Palcross 102 - Honshu Paper Industries). Put two 7cm x 5cm x 1.6cm cut rice cakes and one buckwheat seed package into a 25cm x 32cm nylon-polyethylene laminate bag to make the internal volume about 200ml, then close the bag with a heat seal and keep it at a constant temperature of 25℃. Stored in a container. I created 5 identical materials and 1 of them was 0.
This was used as a day control. In addition, four bags with the same specifications without containing the packaged buckwheat seeds were made and placed in a thermostatic chamber as a control. Every fifth day, one experiment and one control were taken out of the incubator and used for the experiment. The results were as follows.
【表】
吸湿した培養中のそば種子の呼吸作用により餅
のカビ発生は25℃20日間抑制された。
実施例 ２
径15cmのデシケーターの下部（目皿）に径５c.c.
の蒸発皿を置き、蒸発皿中にエスレル10（日産化
学工業……この物質はアルカリ性でエチレンガス
を放出する。）５c.c.と重炭酸ナトリウム２％水溶
液５c.c.とを加え、目皿を置いた。目皿の上に紙
を敷き紙の上にモレキユラル・シーブ（昭和ユ
ノツクス製4Aパウダー）10ｇを置き、デシケー
ターを封じてモレキユラル・シーブにエチレンガ
スを吸収させた。12時間後、モレキユラル・シー
ブを捕集し、和紙に包み、実施例１と同じナイロ
ン−ポリエチレンラミネート袋に入れた。同時に
この袋に籾５ｇを10cm×10cmの予め含水させた不
織布（パルクロス102−本州製紙）に包んだもの
５ケを同封封入して20℃に１晩置き、エチレンガ
スにより籾を活性化させた。実施例１と同じナイ
ロン−ポリエチレンラミネート袋に食パン３枚と
上記籾５ｇを包装したもの１ケと酸素センサー１
ケを入れ内容積を約500mlにした後、袋の口をヒ
ートシールで閉じ25℃の恒温器に収納した。全く
同様の試料を５ケ作製し内１ケを０日目対照とし
た。又、籾を包装したものを収納しない同仕様の
袋４ケを作り対照Ａとして恒温器に入れた。５日
毎に実験、対照それぞれ１ケ宛を恒温器から出し
実験に供した。別に籾５ｇを含水しない不織布に
包んだものを４ケを用意し、含水−エチレン処理
した籾の包装物の代りに食パン、酸素センサーと
共にナイロン−ポリエチレンラミネート袋に入れ
てヒートシールで封じた後、25℃の恒温器に収納
し、対照Ｂとした。この場合の籾はエチレンガス
処理されていないので活性化されていないもので
ある。結果は次の通りであつた。[Table] Mold growth on rice cakes was suppressed for 20 days at 25°C due to the respiration of the buckwheat seeds that absorbed moisture during cultivation. Example 2 A 5 c.c.
Place an evaporating dish, add 5 c.c. of Ethrel 10 (Nissan Chemical Industries...This substance is alkaline and releases ethylene gas) and 5 c.c. of a 2% aqueous solution of sodium bicarbonate into the evaporating dish. I put the plate down. A piece of paper was laid on a perforated plate, 10 g of molecular sieve (4A powder manufactured by Showa Yunotx) was placed on the paper, and the desiccator was sealed to allow the molecular sieve to absorb ethylene gas. After 12 hours, the molecular sieve was collected, wrapped in Japanese paper, and placed in the same nylon-polyethylene laminate bag as in Example 1. At the same time, five bags of 5 g of paddy wrapped in 10 cm x 10 cm of pre-hydrated nonwoven fabric (Palcross 102 - Honshu Paper Industries) were enclosed in this bag and left overnight at 20°C to activate the paddy with ethylene gas. . The same nylon-polyethylene laminate bag as in Example 1 contained 3 slices of bread, 1 bag containing 5 g of the above-mentioned rice, and 1 oxygen sensor.
After filling the bag with water to bring the internal volume to approximately 500 ml, the bag was closed with a heat seal and placed in a thermostat at 25°C. Five identical samples were prepared, and one of them was used as a 0-day control. In addition, four bags with the same specifications without containing the packaged paddy were made and placed in a thermostatic chamber as control A. Every 5 days, one experiment and one control were taken out of the incubator and used for the experiment. Separately, prepare 4 bags of 5g of paddy wrapped in water-free non-woven fabric, put them in a nylon-polyethylene laminate bag with bread and an oxygen sensor instead of the packaged paddy treated with water and ethylene, and seal them with a heat seal. It was stored in a thermostat at 25°C and used as a control B. The rice in this case is not activated because it has not been treated with ethylene gas. The results were as follows.
【表】
吸湿したエチレン処理籾の呼吸作用によりパン
のカビ発生は25℃20日間抑制された。
実施例 ３
ツゲ、マサキ、マキ、ヒイラギ、シダの葉茎部
をそれぞれ５ｇずつ不織布（本州製紙製、パルク
ロス102）に包装し、これと、食パンをナイロン
−ポリエチレンラミネート（グンゼ(株)製26cm×18
cm×0.05mm：酸素透過量35c.c.／24h／１m2）袋に
酸素センサーと共に封入し、ヒートシールで袋口
を閉じ、27℃の恒温槽内に保管した。そして、４
日、８日、12日、16日毎にカビの発生、増殖度
合、並びに酸素センサーの色を観測した。なお、
対照は植物葉茎部を封入しない食パンの包装袋で
ある。
結果は次の通りであつた。[Table] Mold growth on bread was suppressed for 20 days at 25℃ due to the respiration effect of ethylene-treated rice that absorbed moisture. Example 3 5 g of each of the leaves and stems of boxwood, masaki, holly, and fern were wrapped in nonwoven fabric (Palcross 102, manufactured by Honshu Paper Industries), and this and bread were wrapped in a nylon-polyethylene laminate (26 cm × manufactured by Gunze Co., Ltd.). 18
cm x 0.05 mm: Oxygen permeation rate 35 c.c./24 h/1 m 2 ) The bag was sealed together with the oxygen sensor, the bag opening was closed with a heat seal, and the bag was stored in a constant temperature bath at 27°C. And 4
The occurrence of mold, the degree of growth, and the color of the oxygen sensor were observed every day, 8th, 12th, and 16th. In addition,
The control was a bread packaging bag that did not contain plant leaves and stems. The results were as follows.
【表】【table】