JPS60176538A - Sheet for preserving freshness of vegetables - Google Patents

Sheet for preserving freshness of vegetables

Info

Publication number
JPS60176538A
JPS60176538A JP59000144A JP14484A JPS60176538A JP S60176538 A JPS60176538 A JP S60176538A JP 59000144 A JP59000144 A JP 59000144A JP 14484 A JP14484 A JP 14484A JP S60176538 A JPS60176538 A JP S60176538A
Authority
JP
Japan
Prior art keywords
fibers
paper
vegetables
ethylene
freshness
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP59000144A
Other languages
Japanese (ja)
Other versions
JPS6112651B2 (en
Inventor
Buei Haneda
羽田 武栄
Buhei Kono
武平 河野
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to JP59000144A priority Critical patent/JPS60176538A/en
Publication of JPS60176538A publication Critical patent/JPS60176538A/en
Publication of JPS6112651B2 publication Critical patent/JPS6112651B2/ja
Granted legal-status Critical Current

Links

Landscapes

  • Paper (AREA)
  • Storage Of Harvested Produce (AREA)
  • Storage Of Fruits Or Vegetables (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

PURPOSE:To provide the titled sheet with ethylene absorption ability and water absorption ability, by blending short fibers of carbon fiber having ethylene adsorption activity with water suspension of fibrillated cellulose, processing the blend into nonwoven fabric or paper. CONSTITUTION:A cellulosic fiber having high crystallinity is carbonized in an inert gas flow to give a porous carbon fiber. Short fiber of the carbon fiber is treated with a hydrobromide and a dilute acid to give fibers having ethylene adsorption activity. The fibers are blended with an aqueous suspension of fibrillated fibers obtained by beating plant fibers, laid on a drainboard, dehydrated, and dried to give nonwoven fibric or paper.

Description

【発明の詳細な説明】 本発明は、果実の老化抑制及び緑色果菜類の苗化抑制を
行い、高品質の生鮮農産物の安定供給を、長期に渡って
可能ならしめるシート、即ち、2成分系の混合不織布又
は混合紙に関するものである。
DETAILED DESCRIPTION OF THE INVENTION The present invention provides a two-component sheet that suppresses aging of fruits and suppresses seedling formation of green fruits and vegetables, and enables a stable supply of high-quality fresh agricultural products over a long period of time. The present invention relates to a mixed nonwoven fabric or a mixed paper.

周知のようにエチレンは、幅広い生理活性を示す植物ホ
ルモンとして注目されている。そこで、このエチレンの
示す生理活性を有効に利用しようとする試みもまた、活
発に行われている。例えば、エチレン吸収剤はリンゴ、
トマト、及びメロン等の追熟抑制、モモ、カキ等の老化
抑制、並びに、ウメ、カボス及びアスパラガス等の緑色
果菜類の苗化抑制等に大きな効果を示すことが知られて
おり、その実用化が待たれている。エチレン吸収剤とし
ては、先ず過マンガン酸カリウム製剤が開発されたが、
これは安全性の面で問題がある。
As is well known, ethylene has attracted attention as a plant hormone that exhibits a wide range of physiological activities. Therefore, attempts are being made to effectively utilize the physiological activity of ethylene. For example, ethylene absorbers are apples,
It is known to be highly effective in inhibiting ripening of tomatoes and melons, etc., in inhibiting aging in peaches, persimmons, etc., and in inhibiting the formation of seedlings in green fruit vegetables such as plums, kabosu, and asparagus. We are waiting for the transformation. Potassium permanganate preparations were first developed as ethylene absorbers;
This poses a safety problem.

最近、4〜6人の孔径を有する炭素質担体に臭素を吸着
させた製品、並びに、粒状活性炭を臭素酸塩と稀酸とで
処理した製品が開発されている。両者とも安全性の面で
問題がなく、十分実用に供し得るものであり、既に市販
もされている。しかしながら、エチレン処理能力は、前
者が強制循環方式で7 cc’/ g、後者が静置条件
下で27cc/gと少なく、特に後者の場合は黒色粉末
である活性炭を用いるところから、その実用面において
大きく阻害されている。即ち、微粉末の活性炭による当
該果菜類の汚染を防くことができず、別封した紙袋に入
れて隔離し、これを実用に供する等不都合な点が多い。
Recently, products have been developed in which bromine is adsorbed onto a carbonaceous carrier having a pore size of 4 to 6 people, and products in which granular activated carbon is treated with bromate and dilute acid. Both have no problems in terms of safety, can be put to practical use, and are already commercially available. However, the ethylene processing capacity of the former is 7 cc'/g under forced circulation system, and the latter is 27 cc/g under stationary conditions, and in particular, the latter uses activated carbon, which is a black powder, so it is not practical. is greatly hindered. That is, it is not possible to prevent the contamination of the fruits and vegetables by the finely powdered activated carbon, and there are many disadvantages such as having to isolate them in a separately sealed paper bag for practical use.

また、果菜類は密閉して収納する場合が多いが、その際
の腐敗の要因の1つとして、植物自身が放出する水分が
露結し、これがその呼吸作用を妨げるという点が挙げら
れる。そのために古来より、リンゴ等の長期保存のため
に籾穀等が利用されてきている。
In addition, fruits and vegetables are often stored tightly closed, but one of the causes of spoilage is that the moisture released by the plants themselves condenses, which interferes with their respiration. For this reason, rice grains and the like have been used since ancient times for long-term preservation of apples and the like.

上述したところから明らかなように、生鮮農産物の貯蔵
(殊に長期に渡る場合)には、前述のエチレン吸収能以
外に更に、水分吸収能をも具備した物質が最適である。
As is clear from the above, for the storage of fresh agricultural products (particularly for long periods of time), it is best to use a substance that has not only the above-mentioned ethylene absorption ability but also water absorption ability.

本発明はかかる観点からなされたものであって、一般の
包装材として実用性があり、しかもエチレン吸収能と水
分吸収能とを併せ持ち、かつ、柔軟で被覆性のある2成
分系の混合不織布又は混合紙等のシートを提供すること
を目的とするものである。
The present invention has been made from this point of view, and is a two-component mixed nonwoven fabric or a fabric that is practical as a general packaging material, has both ethylene absorption capacity and moisture absorption capacity, and is flexible and coatable. The purpose is to provide sheets of mixed paper, etc.

本発明の構成要件の第1は、高結晶化度の繊維素繊維を
不活性気流中で炭化して得た多孔質の炭素繊維を用いる
ことである。
The first feature of the present invention is to use porous carbon fibers obtained by carbonizing cellulose fibers with a high degree of crystallinity in an inert air stream.

このような繊維の製造は既に試みられており、市販品の
中には表面積が1000〜1600nr/gと非常に大
きく、また、孔径が5〜100人と極めて小さい細孔を
有するものもある。このことは、通常の粒状活性炭に比
較して、その吸着容量ないし吸着速度が数10倍に達す
る素地を有することを意味している。
Attempts have already been made to produce such fibers, and some commercial products have extremely large surface areas of 1000 to 1600 nr/g and extremely small pores of 5 to 100 nr/g in pore diameter. This means that the material has an adsorption capacity or adsorption rate several ten times higher than that of ordinary granular activated carbon.

本発明の構成要件の第2は、このような炭素繊維の短繊
維を公知の臭素酸塩と稀酸とで処理することによって、
エチレンを選択的に吸着固定させ得る短繊維となすこと
である。
The second feature of the present invention is that by treating such short carbon fibers with a known bromate and dilute acid,
The purpose is to create short fibers that can selectively adsorb and fix ethylene.

既に、粒状活性炭を臭素酸塩と稀酸とで処理して、これ
にエチレン吸収能を付与し、これを薄い紙袋に密封した
ものが、果菜類の鮮度保持剤として市販されている。し
たがって、活性表面を持つ炭素物質にエチレン吸収能を
付与する処理方法については、詳しい検討がなされてい
る。即ち、その際の反応主剤である臭素酸塩としてはカ
リウム塩がよく、その濃度は、溶解度が許す限り高濃度
が望ましいこと、また反応助剤としては硫酸が有効であ
り、その濃度は0.5モル前後が最適であること等が知
られている。
Granular activated carbon has already been treated with a bromate and a dilute acid to give it ethylene absorption ability, and the resulting product sealed in a thin paper bag is commercially available as a freshness-preserving agent for fruits and vegetables. Therefore, detailed studies have been made on processing methods for imparting ethylene absorption ability to carbon materials having active surfaces. That is, the bromate that is the main reaction agent in this case is preferably a potassium salt, and its concentration is preferably as high as solubility allows, and sulfuric acid is effective as a reaction aid, and its concentration is 0. It is known that around 5 mol is optimal.

本発明の構成要件の第3は、このようにして得たエチレ
ン吸着活性の炭素繊維の短繊維と、植物繊維を叩解して
得たフィブリル化した繊維素の水懸濁液とを混合し、次
いでこれを簀の上に薄く敷いて脱水し、乾燥処理して不
織布又は紙とするものである。
The third component of the present invention is to mix the thus obtained short fibers of carbon fiber with ethylene adsorption activity and an aqueous suspension of fibrillated cellulose obtained by beating plant fibers, This is then spread thinly on a screen, dehydrated, and dried to produce nonwoven fabric or paper.

この際にフィブリル化した繊維素は、よくバインダーと
しての役割を果たし、例えば抄紙機を用いてこの作業を
行うときには、脱落する炭素繊維が全くなく、しかも柔
軟で弾力性に富んだ不織布ないし紙を得ることができる
。また、その際に使用する植物繊維としては、一般のパ
ルプ液を用いることもできるが、和紙に賞用されている
靭皮繊維が極めて有効である。いずれにしても、当該炭
素繊維に対して10パーセント以上添加することにより
、バインダーとしての役割を果たすことが可能となる。
The fibrillated cellulose in this process often plays a role as a binder, and when this process is performed using a paper machine, for example, there are no carbon fibers that fall off, and it is possible to produce soft and elastic non-woven fabrics or paper. Obtainable. Further, as the vegetable fibers used in this case, general pulp liquid can be used, but bast fibers, which are used in Japanese paper, are extremely effective. In any case, by adding 10% or more to the carbon fiber, it becomes possible to play a role as a binder.

不織布及び紙製造時の水懸濁液の濃度は、1パ一セント
前後とすることが、作業性の面から上限といえる。
From the viewpoint of workability, the upper limit of the concentration of the water suspension during the production of nonwoven fabrics and paper is about 1%.

勿論抄紙の際と同じように、この濃度を薄くし、かつ、
フィブリル化した繊維素置の比率を多くすれば、柔軟性
並びにクッション性は劣るが、引裂き強度の大きい炭素
繊維との混合不織布ないし混合紙かえられる。また、予
め活性炭素繊維とフィブリル化した繊維素とを混合して
、抄紙の要領にて不織布ないし紙となし、これに本発明
の構成要件第2に示した臭素酸塩−補値酸処理を行って
も、その鮮度保持効果に大差はない。活性炭素繊維とフ
ィブリル化繊維素との混合の際に重要なことは、その混
合比率が果菜類の密閉収納時においては大きな影響を与
えるということである。即ち、繊維素の水分吸収能によ
って水蒸気の露結が防止されるということである。殊に
、合成樹脂製の薄膜からなる袋等に果菜類を入れ、密封
して保存する場合等には(通称ビニールパック)、露結
した水分による早期腐敗が問題となる。したがって、フ
ィブリル化繊維素の混合率を50パ一セント前後にする
と、このような密閉貯蔵の場合に、その鮮度保持能力が
倍加される。
Of course, just like when making paper, this density is reduced, and
If the proportion of fibrillated fibers is increased, the flexibility and cushioning properties will be inferior, but a mixed nonwoven fabric or mixed paper with carbon fiber, which has a high tear strength, can be used. In addition, activated carbon fibers and fibrillated cellulose are mixed in advance to form a nonwoven fabric or paper in the manner of paper making, and this is subjected to the bromate-complementary acid treatment shown in the second component of the present invention. Even if you do, there is not much difference in the freshness preservation effect. What is important when mixing activated carbon fibers and fibrillated cellulose is that the mixing ratio has a large effect on the sealed storage of fruits and vegetables. In other words, the moisture absorption ability of cellulose prevents water vapor from condensing. In particular, when fruits and vegetables are placed in a bag made of a thin synthetic resin film and stored tightly sealed (commonly known as a vinyl pack), premature spoilage due to dew condensation becomes a problem. Therefore, when the mixing ratio of fibrillated cellulose is around 50 percent, the freshness retention capacity is doubled in case of such closed storage.

以上述べた諸方法により作製された不織布又は紙等のシ
ートのエチレン処理能力を、エチレンと当該吸収剤とを
密閉してその圧力低下から検討した結果、炭素分の同重
量においては、前述の市販の粒状活性炭を処理した吸収
剤の10倍以上に達することが推定された。このことは
、本発明の構成要件第2及び第3の処理法が適切であり
、出発原料である活性炭素繊維の表面及び細孔等の組織
を損なうことなく、エチレン吸収能を付与し得たこと示
している。このことはまた、本発明に係るシートが、果
菜類から発生するエチレンを迅速かつ確実に吸収して、
従来品以上に果菜類の長期保存に有効であることを示唆
している。また、混合した繊維素の水分吸収能との相乗
効果による、すぐれた鮮度保持効果を期待することがで
きる。更に、このようにして得たシートは、対象とする
果菜類を何ら汚染することなく、直接当接させることが
できる。そのために例えば、シートを袋状にして果菜全
体を直接包むとか、あるいは、布状にして果菜類の収納
箱の下に敷いたり、または、上部全体を覆ったりし、以
て発生するエチレン及び水分等を均等にかつ迅速に吸収
させることが可能となる。それと同時に、その柔軟性及
びクッション性により、特に果菜類の輸送時における機
械的要因による不良果実の発生を、最小限に抑えること
も可能となる。
As a result of examining the ethylene processing capacity of sheets of nonwoven fabric or paper produced by the various methods described above from the pressure drop when ethylene and the absorbent are sealed, it was found that, at the same weight of carbon content, It was estimated that the absorption capacity was more than 10 times that of the absorbent treated with granular activated carbon. This indicates that the second and third treatment methods of the present invention were appropriate and were able to impart ethylene absorption ability without damaging the surface and pore structure of the activated carbon fiber, which is the starting material. It shows that. This also means that the sheet according to the present invention can quickly and reliably absorb ethylene generated from fruits and vegetables.
This suggests that it is more effective than conventional products for long-term preservation of fruits and vegetables. In addition, an excellent freshness-keeping effect can be expected due to the synergistic effect with the moisture absorption ability of the mixed cellulose. Furthermore, the sheet obtained in this manner can be brought into direct contact with target fruits and vegetables without any contamination. For this purpose, for example, the sheet may be made into a bag and wrapped directly around the whole fruit or vegetables, or it may be made into a cloth and placed under the storage box for fruit and vegetables, or the entire top may be covered, and the ethylene and moisture generated thereby. etc. can be absorbed evenly and quickly. At the same time, its flexibility and cushioning properties make it possible to minimize the occurrence of defective fruits due to mechanical factors, especially during transportation of fruits and vegetables.

次に具体的実施例を挙げて、更に本発明の有用性を実証
する。
Next, specific examples will be given to further demonstrate the usefulness of the present invention.

〔実施例1〕 300ccの0.5モル稀硫酸水溶液に50gの臭素酸
カリウムを加え、50度Cに加温してよく攪拌溶解せし
めた。この水溶液に、高結晶化度の繊維素繊維を炭化処
理した太さ1.5デニール、長さ3乃至5ミリメートル
の活性炭素繊維(市販名:活性炭素繊維KF)の短繊維
10gを投入した。反応は発熱反応であり、水溶液の温
度は投入直後から上昇し始め、2分後には60度Cに達
した。温度上昇完了後、10分間更に放置した。次いで
この短繊維を取り出し、水洗並びに脱水を3回繰り返し
て反応残液を除去した。次に長さ10ミリメートル前後
の亜麻繊維くず1,5gを50ccの水に懸濁し、これ
を乳鉢を用いてよく叩解し、フィブリル化繊維素の水エ
マルジョンを得た。このエマルジョンに、先に化学処理
した活性炭素繊維10gと水1000ccとを加えて十
分攪拌し、これを紙料として、抄紙法の要領にて竹管の
上に均一に沈積せしめた。水切後105度Cにて乾燥し
、厚さ0.5ミリメートル、面積600平方センチメー
トルのクッション性にすぐれた黒色不織布を得た。そし
て、この不織布を幅2センチメートル、長さ20センチ
メートルで重量約1gの細片に切断し、この細片を試料
として野菜の鮮度保持効果を、市販の鮮度保持剤と比較
しつつ検討した。
[Example 1] 50 g of potassium bromate was added to 300 cc of a 0.5 molar dilute sulfuric acid aqueous solution, heated to 50° C., and stirred well to dissolve. To this aqueous solution, 10 g of activated carbon fiber short fibers (commercial name: activated carbon fiber KF) having a thickness of 1.5 denier and a length of 3 to 5 mm, which were carbonized cellulose fibers with a high degree of crystallinity, were added. The reaction was exothermic, and the temperature of the aqueous solution began to rise immediately after it was added, reaching 60 degrees Celsius after 2 minutes. After the temperature had finished rising, it was left to stand for an additional 10 minutes. Next, the short fibers were taken out, washed with water and dehydrated three times to remove the reaction residual liquid. Next, 1.5 g of flax fiber waste having a length of about 10 mm was suspended in 50 cc of water and thoroughly beaten using a mortar to obtain a water emulsion of fibrillated cellulose. 10 g of the previously chemically treated activated carbon fibers and 1000 cc of water were added to this emulsion and thoroughly stirred, and this was used as a paper stock and deposited uniformly on a bamboo tube according to the papermaking method. After draining, it was dried at 105 degrees Celsius to obtain a black nonwoven fabric with excellent cushioning properties and a thickness of 0.5 mm and an area of 600 square centimeters. This nonwoven fabric was then cut into strips 2 cm wide, 20 cm long, and weighing about 1 g, and the strips were used as samples to examine their effectiveness in preserving the freshness of vegetables by comparing them with commercially available freshness preserving agents. .

先ず、大分市において昭和58年12月4日に収穫した
ニラ5kgを同年12月6日1 、25kg宛4等分し
、その1群は自然放置し、他の3群は、それぞれ厚さ2
5ミクロンのポリエチレンフィルム袋に収納して密閉し
た。その中の1つには、同時に市販の鮮度保持剤である
グリーンパック5g入り袋(活性炭とゼオライトより構
成されたもの)を、また、他の】つには、市販の活性炭
素を臭素酸塩−稀酸系で処理した5g入り袋(本州製紙
株式会社製)を、そして残りの1つには、前記本発明に
係る混合不織布の細片1gを入れた。なお、ビニール袋
内のエチレン発生を助長する目的で、上記の外に各袋内
に、既に腐敗の始まっているニラを1株宛入れて腐敗化
を促進させた。これらの試験試料は、いずれも15度C
程度の室温下に放置した。その結果、先ず同年12月9
日に至り、自然放置したものの葉に背比が起り、腐敗の
始まったことが確認された。次いで同年12月10日に
至り、グリーンパックを入れたものに、また、同年12
月13日に至り活性炭を臭素酸塩−稀酸処理したものを
入れたものに、それぞれ葉の背比が始まった。これに対
して本発明に係るものにおいては、更に7日間経過した
12月20日にようやく葉の背比が始まった。
First, on December 6th of the same year, 5 kg of chives harvested in Oita City on December 4, 1980 were divided into four equal parts of 25 kg each, one group was left to naturally grow, and the other three groups were each divided into 25 kg pieces.
It was placed in a 5 micron polyethylene film bag and sealed. One of them contained a 5g bag of Green Pack (composed of activated carbon and zeolite), which is a commercially available freshness preserving agent, and the other contained a bag containing commercially available activated carbon with bromate. - A 5 g bag (manufactured by Honshu Paper Industries Co., Ltd.) treated with a dilute acid system was placed in the bag, and 1 g of the mixed nonwoven fabric according to the present invention was placed in the remaining bag. In addition, in order to promote the generation of ethylene in the plastic bags, in addition to the above, one chive plant that had already started to rot was placed in each bag to promote rotting. All of these test samples were heated to 15 degrees C.
It was left at room temperature. As a result, on December 9th of the same year,
By the end of the day, the leaves that had been left to grow began to curl, indicating the beginning of rot. Then, on December 10th of the same year, the green pack was added, and on December 10th of the same year,
On the 13th of May, the height of leaves began to change in the activated carbon treated with bromate and dilute acid. On the other hand, in the plants according to the present invention, leaf height finally started to change on December 20th, after a further 7 days had passed.

次に同様な手法で、ブロッコリーの鮮度保持効果を検討
した。
Next, we used a similar method to examine the effect of keeping broccoli fresh.

即ち、鳥取県中出回において昭和58年12月3日に収
穫したブロッコリー7、5kgを同年12月6日に4等
分し、ニラの場合と同様にしてそれぞれの鮮度保持能力
を、ブロッコリーの開花時期を目安にして判定した。但
し、ビニール袋中に同封する前出の市販の鮮度保持剤は
、ニラの場合と同様に5g入り袋をそれぞれ1個宛用い
たが、本発明に係る不織布については0.5gを用いた
。その結果、先ず自然放置のものは同年12月8日に、
また、グリーンパンク入りのものは同年12月10日に
、そして、活性炭を臭素酸塩−稀酸系で処理したものを
入れたものは、同年12月12日に至ってそれぞれ開花
し始め、商品価値を失なった。これに対して本発明に係
るものは、同年12月25日に至ってようやく開花した
In other words, 7.5 kg of broccoli harvested on December 3, 1982 at Tottori Prefecture Chudekai was divided into four equal parts on December 6 of the same year, and the freshness retention ability of each was measured in the same way as for chives. Judgment was made using the flowering time as a guide. However, as for the above-mentioned commercially available freshness-preserving agent enclosed in a plastic bag, one bag containing 5 g was used for each bag as in the case of chives, but 0.5 g was used for the nonwoven fabric according to the present invention. As a result, first of all, on December 8th of the same year,
In addition, those containing green puncture began to bloom on December 10th of the same year, and those containing activated carbon treated with a bromate-dilute acid system began blooming on December 12th of the same year, and their commercial value increased. lost. In contrast, the plants according to the present invention finally bloomed on December 25th of the same year.

これらの例からして本発明に係るシートは、野菜の鮮度
保持に、従来品と比較して抜群の効果を発揮することが
明らかになった。
From these examples, it is clear that the sheet according to the present invention exhibits an outstanding effect in preserving the freshness of vegetables compared to conventional products.

〔実施例2〕 高結晶化度の繊維素繊維を出発原料とした活性炭素繊維
30パーセント、及び、フィブリル化した繊維素の短繊
維70パーセントからなる市販の活性炭素繊維KFペー
パー3g(厚さ250 ミクロン、面積450平方セン
チメートル)を採り、これを臭素酸カリウム15重量パ
ーセントを含んだ0.5モルの補値酸水溶液150cc
に10分間浸積した。投入前の水溶液の温度は40度C
であり、KFペーパー浸積直後より温度は急速に上昇し
始め、2分後4こは50度Cまで達した。脱水及び水洗
を3回繰り返し、反応残液の除去を行い、次いで105
度Cで乾燥して水分を除去した。また、この処理によっ
て出発原料のKFペーパーはより柔軟性を増し、被覆性
の向上が認められた。この処理ペーパーを用い15度C
前後の室温下におけるリンゴ、柿及びトマトの鮮度保持
効果を調べた。即ち、昭和58年12月1日、市販の長
野県産スターリンゴ、山梨県産富有柿及び愛知県産ファ
ーストトマトそれぞれ6個を3等分し、その1群を自然
放置した。また、他の1群を、実施例1で作製した不織
布1gとともにビニール袋内に密封した。そして、最後
の1群は、本実施例にて作製したKFペーパー処理のも
のを、当該果実等の上面を直接覆うように被せるだけに
して、解放下に室温放置した。かくして2週間経過後の
同年12月14日に、鮮度保持の状態を観察した。先ず
自然放置のものは、トマト及び柿ともがくは緑色並びに
柔軟性を失い、果肉は軟化が進んで植物体を失なってい
た。また、リンゴは果面が一部褐色に変化するとともに
、 柄が枯れていた。これに対して、本発明に係る混合
不織布並びムこKFペーパー処理のものを用いたものは
、両者ともトマト及び柿について一部変色が見られたも
のの、保存状態は良好であって商品価値を失なうまでに
は至っていなかった。
[Example 2] 3 g of commercially available activated carbon fiber KF paper (thickness 250 micron, area 450 square centimeters), and add it to 150 cc of a 0.5 mol complementary acid aqueous solution containing 15% by weight of potassium bromate.
immersed in water for 10 minutes. The temperature of the aqueous solution before injection is 40 degrees C.
Immediately after the KF paper was immersed, the temperature began to rise rapidly and reached 50 degrees Celsius in 4 cases after 2 minutes. Dehydration and water washing were repeated three times to remove the reaction residue, and then 105
The water was removed by drying at 30°C. Furthermore, this treatment made the starting material KF paper more flexible, and it was observed that the coating properties were improved. 15 degrees C using this treated paper
The freshness retention effect of apples, persimmons, and tomatoes at room temperature before and after was investigated. That is, on December 1, 1981, six commercially available star apples from Nagano Prefecture, Fuyu persimmons from Yamanashi Prefecture, and first tomatoes from Aichi Prefecture were each divided into three equal parts, and one group was left to stand. In addition, another group was sealed in a plastic bag together with 1 g of the nonwoven fabric produced in Example 1. In the last group, the KF paper-treated fruit prepared in this example was simply placed on the upper surface of the fruit, etc., and left open at room temperature. Two weeks later, on December 14 of the same year, the state of freshness maintenance was observed. First, tomatoes and persimmons that were left to grow lost their green color and flexibility, and their pulps softened and lost their plant bodies. In addition, part of the apple's fruit surface had turned brown, and the stalk had withered. On the other hand, in the case of the mixed nonwoven fabric according to the present invention and the one treated with Muco KF paper, although some discoloration was observed in tomatoes and persimmons, the storage condition was good and the commercial value was low. I hadn't gotten to the point where I lost it.

また、リンゴの場合は完全な状態を維持し、柄も買入れ
時と変らなかった。
In addition, the apples remained in perfect condition and the handles were the same as when they were purchased.

以上のように本発明に係るものは、活性炭を基材とした
エチレン吸収能を有する鮮度保持剤と違って、果実全面
に渡って被覆可能なため、特に解放下であってム密閉時
の場合と略同等の鮮度保持効果を持つことが判明した。
As described above, unlike the freshness-preserving agent that is based on activated carbon and has ethylene absorption ability, the product according to the present invention can coat the entire surface of the fruit, especially when the fruit is open and closed. It was found that it has approximately the same freshness retention effect as

また、実施例1におけるブロッコリーの鮮度保持の比較
実験において、実施例2で作製したKFペーパー処理の
ものL5g (含有炭素繊維0.5g)を実施例1の混
合不織布の代わりに用いた場合には、鮮度保持期間は更
に2週間程度延長され、略1カ月間の長期に渡り開花を
見ず、その鮮度が保持されることが確認された。これは
、ペーパー内に多量に含有された繊維素繊維の水分吸収
能による相乗効果によるものと考えられる。
In addition, in a comparative experiment of maintaining the freshness of broccoli in Example 1, when 5 g of the KF paper-treated broccoli produced in Example 2 (containing 0.5 g of carbon fiber) was used instead of the mixed nonwoven fabric of Example 1, The freshness retention period was further extended by about two weeks, and it was confirmed that the freshness was maintained without blooming for a long period of about one month. This is thought to be due to the synergistic effect of the water absorbing ability of the cellulose fibers contained in the paper in large amounts.

手続補正書 昭和59年9県呻日 特許庁長官 志賀 学 殿 1 事件の表示 昭和59年特許 願第144 号 2、発明の名称 果菜類の鮮度保持用シート3、 補正
をする者 事件との関係 特許出願人 住 所 山梨県富士吉田市上吉田3814番地氏 名(
名称) 羽 1) 武 栄 4、代理人 6、 補正により増加する発明の数 1明 細 書 1、発明の名称 炭素繊維及びこれを利用した果菜類の鮮度保持用シート 2、特許請求の範囲 (1)高結晶化度の繊維素繊維を炭化処理して得られる
多孔質の炭素繊維の短繊維に、臭素酸塩−稀酸水溶液処
理を施して得た炭素繊維。
Procedural amendment written by Manabu Shiga, Commissioner of the Japan Patent Office, 9th Prefecture, 1980 1 Indication of the case 1989 Patent Application No. 144 2, Title of the invention Sheet for preserving the freshness of fruits and vegetables 3 Relationship between the person making the amendment and the case Patent applicant address: 3814 Kamiyoshida, Fujiyoshida City, Yamanashi Prefecture Name (
Name) Feather 1) Ei Take 4, Agent 6, Number of inventions increased by amendment 1 Specification 1, Name of invention Carbon fiber and sheet for keeping fruits and vegetables fresh using the same 2, Claims ( 1) Carbon fiber obtained by subjecting porous carbon fiber short fibers obtained by carbonizing cellulose fibers with high crystallinity to a bromate-dilute acid aqueous solution treatment.

(2)高結晶化度の繊維素繊維を炭化処理して得られる
多孔質の炭素繊維の短繊維に、臭素酸塩−稀酸水溶液処
理を施して得た炭素繊維と、フィブリル化した繊維素と
からなる果菜類の鮮度保持用シート。
(2) Carbon fibers obtained by subjecting short fibers of porous carbon fibers obtained by carbonizing high-crystallinity cellulose fibers to bromate-dilute acid aqueous solution treatment and fibrillated cellulose fibers. A sheet for preserving the freshness of fruits and vegetables.

3、発明の詳細な説明 本発明は、炭素繊維、並びに、果実の老化抑制及び緑色
果菜類の苗化抑制を行い、高品質の生鮮農産物の安定供
給を、長期に渡って可能ならしめるシート、即ち、2成
分系の混合不織布又は混合紙に関するものである。
3. Detailed Description of the Invention The present invention provides carbon fiber and a sheet that suppresses the aging of fruits and the formation of seedlings of green fruits and vegetables, and enables a stable supply of high-quality fresh agricultural products over a long period of time. That is, it relates to a two-component mixed nonwoven fabric or mixed paper.

周知のようにエチレンは、幅広い生理活性を示す植物ホ
ルモンとして注目されている。そこで、このエチレンの
示す生理活性を有効に利用しようとする試みもまた、活
発に行われている。
As is well known, ethylene has attracted attention as a plant hormone that exhibits a wide range of physiological activities. Therefore, attempts are being made to effectively utilize the physiological activity of ethylene.

例えば、エチレン吸収剤はリンゴ、トマト、及びメロン
等の追熟抑制、モモ、カキ等の老化抑制、並びに、ウメ
、カボス及びアスパラガス等の緑色果菜類の苗化抑制等
に大きな効果を示すことが知られており、その実用化が
待たれている。エチレン吸収剤としては、先ず過マンガ
ン酸カリウム製剤が開発されたが、これば安全性の面で
問題がある。
For example, ethylene absorbers are highly effective in inhibiting ripening of apples, tomatoes, melons, etc., inhibiting aging of peaches, persimmons, etc., and inhibiting seedling formation of green fruit vegetables such as plums, kabosu, and asparagus. is known, and its practical application is awaited. As an ethylene absorbent, a potassium permanganate preparation was first developed, but this had problems in terms of safety.

最近、4〜6人の孔径を有する炭素質担体に臭素を吸着
させた製品、並びに、粒状活性炭を臭素酸塩と稀酸とで
処理した製品が開発されている。両者とも安全性の面で
問題がなく、十分実用に供し得るものであり、既に市販
もされている。しかしながら、エチレン処理能力は、前
者が強制循環方式で7cc/g、後者が静置条件下で2
7cc/gと少なく、特に後者の場合は黒色粉末である
活性炭を用いるところから、その実用面において大きく
阻害されている。即ち、微粉末の活性炭による当該果菜
類の汚染を防ぐことができず、別封した紙袋に入れて隔
離し、これを実用に供する等不都合な点が多い。また、
果菜類は密閉して収納する場合が多いが、その際の腐敗
の要因の1つとして、植物自身が放出する水分が露結し
、これがその呼吸作用を妨げるという点が挙げられる。
Recently, products have been developed in which bromine is adsorbed onto a carbonaceous carrier having a pore size of 4 to 6 people, and products in which granular activated carbon is treated with bromate and dilute acid. Both have no problems in terms of safety, can be put to practical use, and are already commercially available. However, the ethylene processing capacity of the former is 7 cc/g under forced circulation method, and the latter is 2 cc/g under static conditions.
The amount of activated carbon is as low as 7 cc/g, and especially in the latter case, black powder activated carbon is used, which greatly hinders its practical use. That is, it is not possible to prevent contamination of the fruits and vegetables by the finely powdered activated carbon, and there are many disadvantages such as having to isolate them in a separately sealed paper bag for practical use. Also,
Fruits and vegetables are often stored tightly closed, but one of the causes of spoilage is that the moisture released by the plants themselves condenses, which interferes with their respiration.

そのために古来より、リンゴ等の長期保存のために籾穀
等が利用されてきている。
For this reason, rice grains and the like have been used since ancient times for long-term preservation of apples and the like.

上述したところから明らかなように、生鮮農産物の貯蔵
(殊に長期に渡る場合)には、前述のエチレン吸収能以
外に更に、水分吸収能をも具備した物質が最適である。
As is clear from the above, for the storage of fresh agricultural products (particularly for long periods of time), it is best to use a substance that has not only the above-mentioned ethylene absorption ability but also water absorption ability.

本発明はかかる観点からなされたものであって、一般の
包装材として実用性があり、しかもエチレン吸収能と水
分吸収能とを併せ持ち、かつ、柔軟で被覆性のある2成
分系の混合不織布又は混合紙等のシート及びこのシート
を生成するための炭素繊維を提供することを目的とする
ものである。
The present invention has been made from this point of view, and is a two-component mixed nonwoven fabric or a fabric that is practical as a general packaging material, has both ethylene absorption capacity and moisture absorption capacity, and is flexible and coatable. The object is to provide a sheet of mixed paper or the like and carbon fiber for producing this sheet.

本発明に係るシートの構成要件の第1は、高結晶化度の
繊維素繊維を不活性気流中で炭化して得た多孔質の炭素
繊維を用いることである。
The first constituent feature of the sheet according to the present invention is to use porous carbon fibers obtained by carbonizing cellulose fibers with a high degree of crystallinity in an inert air stream.

このような繊維の製造は既に試みられており、市販品の
中には表面積が1000〜1600 of /gと非常
に大きく、また、孔径が5〜100人と極めて小さい細
孔を有するものもある。このことは、通常の粒状活性炭
に比較して、その吸着容量ないし吸着速度が数10倍に
達する素地を有することを意味している。
Attempts have already been made to manufacture such fibers, and some commercially available products have extremely large surface areas of 1000 to 1600 of/g, and some have extremely small pores of 5 to 100 pores in diameter. . This means that the material has an adsorption capacity or adsorption rate several ten times higher than that of ordinary granular activated carbon.

本発明に係るシートの構成要件の第2は、このような炭
素繊維の短繊維を公知の臭素酸塩と稀酸とで処理するこ
とによって、エチレンを選択的に吸着固定させ得る短繊
維となすことである。
The second constituent feature of the sheet according to the present invention is that short fibers of such carbon fibers are treated with a known bromate and a dilute acid to form short fibers that can selectively adsorb and fix ethylene. That's true.

既に、粒状活性炭を臭素酸塩と稀酸とで処理して、これ
にエチレン吸収能を付与し、これを薄い紙袋に密封した
ものが、果菜類の鮮度保持剤として市販されている。し
たがって、活性表面を持つ炭素物質にエチレン吸収能を
付与する処理方法については、詳しい検討がなされてい
る。即ち、その際の反応主剤である臭素酸塩としてはカ
リウム塩がよく、その濃度は、溶解度が許す限り高濃度
が望ましいこと、また反応助剤としては硫酸が有効であ
り、その濃度は0.5モル前後が最適であること等が知
られている。
Granular activated carbon has already been treated with a bromate and a dilute acid to give it ethylene absorption ability, and the resulting product sealed in a thin paper bag is commercially available as a freshness-preserving agent for fruits and vegetables. Therefore, detailed studies have been made on processing methods for imparting ethylene absorption ability to carbon materials having active surfaces. That is, the bromate that is the main reaction agent in this case is preferably a potassium salt, and its concentration is preferably as high as solubility allows, and sulfuric acid is effective as a reaction aid, and its concentration is 0. It is known that around 5 mol is optimal.

本発明に係るシートの構成要件の第3は、このようにし
て得たエチレン吸着活性の炭素繊維の短繊維と、植物繊
維を叩解して得たフィブリル化した繊維素の水懸濁液と
を混合し、次いでこれを簀の上に薄く敷いて脱水し、乾
燥処理して不織布又は紙とするものである。
The third component of the sheet according to the present invention is that the short fibers of carbon fibers with ethylene adsorption activity thus obtained are combined with an aqueous suspension of fibrillated cellulose obtained by beating vegetable fibers. The mixture is mixed, then spread thinly on a screen, dehydrated, and dried to produce nonwoven fabric or paper.

この際にフィブリル化した繊維素は、よくバインダーと
しての役割を果たし、例えば抄紙機を用いてこの作業を
行うときには、脱落する炭素繊維が全(なく、しかも柔
軟で弾力性に富んだ不織布ないし紙を得ることができる
。また、その際に使用する植物繊維としては、一般のパ
ルプ液を用いることもできるが、和紙に賞用されている
靭皮繊維が極めて有効である。いずれにしても、当該炭
素繊維に対して10パーセント以上添加することにより
、バインダーとしての役割を果たすことが可能となる。
The fibrillated cellulose in this process often plays a role as a binder, and when this process is carried out using a paper machine, for example, all the carbon fibers that fall off are removed, and they are made of soft and highly elastic non-woven fabric or paper. In addition, as the vegetable fiber used in this case, general pulp liquid can be used, but bast fiber, which is used for Japanese paper, is extremely effective.In any case, By adding 10% or more to the carbon fiber, it becomes possible to play a role as a binder.

不織布及び紙製造時の水!il!濁液の濃度は、1パ一
セント前後とすることが、作業性の面から上限といえる
Water during non-woven fabric and paper manufacturing! Il! From the viewpoint of workability, it can be said that the upper limit of the concentration of the turbid liquid is around 1%.

勿論抄紙の際と同じように、この濃度を薄くし、かつ、
フィブリル化した繊維素置の比率を多くすれば、柔軟性
並びにクッション性は劣るが、引裂き強度の大きい炭素
繊維との混合不織布ないし混合紙かえられる。また、予
め活性炭素繊維とフィブリル化した繊維素とを混合して
、抄紙の要領にて不織布ないし紙となし、これに本発明
の構成要件第2に示した臭素酸塩−補値酸処理を行って
も、その鮮度保持効果に大差はない。活性炭素繊維とフ
ィブリル化繊維素との混合の際に重要なことは、その混
合比率が果菜類の密閉収納時においては大きな影響を与
えるということである。即ち、繊維素の水分吸収能によ
って水蒸気の露結が防止されるということである。殊に
、合成樹脂製の薄膜からなる袋等に果菜類を入れ、密封
して保存する場合等には(通称ビニールパンク)、露結
した水分による早期腐敗が問題となる。したがって、フ
ィブリル化繊維素の混合率を50パ一セント前後にする
と、このような密閉貯蔵の場合に、その鮮度保持能力が
倍加される。
Of course, just like when making paper, this density is reduced, and
If the proportion of fibrillated fibers is increased, the flexibility and cushioning properties will be inferior, but a mixed nonwoven fabric or mixed paper with carbon fiber, which has a high tear strength, can be used. In addition, activated carbon fibers and fibrillated cellulose are mixed in advance to form a nonwoven fabric or paper in the manner of paper making, and this is subjected to the bromate-complementary acid treatment shown in the second component of the present invention. Even if you do, there is not much difference in the freshness preservation effect. What is important when mixing activated carbon fibers and fibrillated cellulose is that the mixing ratio has a large effect on the sealed storage of fruits and vegetables. In other words, the moisture absorption ability of cellulose prevents water vapor from condensing. In particular, when fruits and vegetables are placed in bags made of thin synthetic resin membranes and stored tightly sealed (commonly known as vinyl punctures), early spoilage due to dew condensation becomes a problem. Therefore, when the mixing ratio of fibrillated cellulose is around 50 percent, the freshness retention capacity is doubled in case of such closed storage.

以上述べた縫方法により作製された不織布又は紙等のシ
ートのエチレン処理能力を、エチレンと当該吸収剤とを
密閉してその圧力低下から検討した結果、炭素分の同重
量においては、前述の市販の粒状活性炭を処理した吸収
剤の10倍以上に達することが推定された。このことは
、本発明の構成要件第2及び第3の処理法が適切であり
、出発原料である活性炭素繊維の表面及び細孔等の組織
を損なうことな(、エチレン吸収能を付与し得たこと示
している。このことはまた、本発明に係るシートが、果
菜類から発生するエチレンを迅速かつ確実に吸収して、
従来品以上に果菜類の長期保存に有効であることを示唆
している。また、混合した繊維素の水分吸収能との相乗
効果による、すぐれた鮮度保持効果を期待することがで
きる。更に、このようにして得たシートは、対象とする
果菜類を何ら汚染することなく、直接当接させることが
できる。
As a result of examining the ethylene processing capacity of a sheet of nonwoven fabric or paper produced by the sewing method described above from the pressure drop when ethylene and the absorbent are sealed, it was found that, at the same weight of carbon content, It was estimated that the absorption capacity was more than 10 times that of the absorbent treated with granular activated carbon. This means that the second and third treatment methods of the present invention are appropriate and do not damage the structure of the activated carbon fibers, such as the surface and pores, of the starting material. This also shows that the sheet according to the present invention can quickly and reliably absorb ethylene generated from fruits and vegetables.
This suggests that it is more effective than conventional products for long-term preservation of fruits and vegetables. In addition, an excellent freshness-keeping effect can be expected due to the synergistic effect with the moisture absorption ability of the mixed cellulose. Furthermore, the sheet obtained in this manner can be brought into direct contact with target fruits and vegetables without any contamination.

そのために例えば、シートを袋状にして果菜全体を直接
包むとか、あるいは、布状にして果菜類の収納箱の下に
敷いたり、または、上皿全体を覆ったりし、以て発生す
るエチレン及び水分等を均等にかつ迅速に吸収させるこ
とが可能となる。それと同時に、その柔軟性及びクッシ
ョン性により、特に果菜類の輸送時における機械的要因
による不良果実の発生を、最少限に抑えることも可能と
なる。
For this purpose, for example, the sheet may be made into a bag and wrapped directly around all the fruits and vegetables, or it may be made into a cloth and placed under the storage box for fruits and vegetables, or the sheet may be placed over the entire upper tray, thereby reducing the amount of ethylene generated. It becomes possible to absorb moisture etc. evenly and quickly. At the same time, its flexibility and cushioning properties make it possible to minimize the occurrence of defective fruits due to mechanical factors, especially during transportation of fruits and vegetables.

次に具体的実施例を挙げて、更に本発明の有用性を実証
する。
Next, specific examples will be given to further demonstrate the usefulness of the present invention.

〔実施例1〕 300ccの0.5モル稀硫酸水溶液に50gの臭素酸
カリウムを加え、50度Cに加温してよく攪拌溶解せし
めた。この水溶液に、高結晶化度の繊維素繊維を炭化処
理した太さ165デニール、長さ3乃至5ミリメートル
の活性炭素繊維(市販名:活性炭素繊維KF)の短繊維
l。
[Example 1] 50 g of potassium bromate was added to 300 cc of a 0.5 molar dilute sulfuric acid aqueous solution, heated to 50° C., and stirred well to dissolve. In this aqueous solution, short fibers of activated carbon fiber (commercial name: activated carbon fiber KF) having a thickness of 165 denier and a length of 3 to 5 mm were added by carbonizing cellulose fibers with a high degree of crystallinity.

gを投入した。反応は発熱反応であり、水溶液の温度は
投入直後から上昇し始め、2分後には60度Cに達した
。温度上昇完了後、10分間更に放置した。次いでこの
短繊維を取り出し、水洗並びに脱水を3回繰り返して反
応残液を除去した。次に長さ10ミリメートル前後の亜
麻繊維くず1.5 gを50ccの水に懸濁し、これを
乳鉢を用いてよく叩解し、フィブリル化繊維素の水エマ
ルジョンを得た。このエマルジョンに、先に化学処理し
た活性炭素繊維10gと水1000ccとを加えて十分
攪拌し、これを紙料として、抄紙法の要領にて竹管の上
に均一に沈積せしめた。水切後105度Cにて乾燥し、
厚さ0.5ミリメートル、面積600平方センチメート
ルのクッション性にすぐれた黒色不織布を得た。そして
、この不織布を@2センチメートル、長さ20センチメ
ートルで重量的1gの細片に切断し、この細片を試料と
して野菜の鮮度保持効果を、市販の鮮度保持剤と比較し
つつ検討した。
g was added. The reaction was exothermic, and the temperature of the aqueous solution began to rise immediately after it was added, reaching 60 degrees Celsius after 2 minutes. After the temperature had finished rising, it was left to stand for an additional 10 minutes. Next, the short fibers were taken out, washed with water and dehydrated three times to remove the reaction residual liquid. Next, 1.5 g of flax fiber waste having a length of about 10 mm was suspended in 50 cc of water and thoroughly beaten using a mortar to obtain a water emulsion of fibrillated cellulose. 10 g of the previously chemically treated activated carbon fibers and 1000 cc of water were added to this emulsion and thoroughly stirred, and this was used as a paper stock and deposited uniformly on a bamboo tube according to the papermaking method. After draining, dry at 105 degrees C.
A black nonwoven fabric having a thickness of 0.5 mm and an area of 600 square centimeters with excellent cushioning properties was obtained. Then, this nonwoven fabric was cut into strips of 2 cm, length 20 cm, and weight 1 g, and the strips were used as samples to examine the freshness-preserving effect of vegetables by comparing them with commercially available freshness-preserving agents. .

先ず、大分市において昭和58年12月4日に収穫した
ニラ5kgを同年12月6日1.25kg宛4等分し、
その1群は自然放置し、他の3群は、それぞれ厚さ25
ミクロンのポリエチレンフィルム袋に収納して密閉した
。その中の1つには、同時に市販の鮮度保持剤であるグ
リーンパンク5g入り袋(活性炭とゼオライトより構成
されたもの)を、また、他の1つには、市販の活性炭素
を臭素酸塩−稀酸系で処理した5g入り袋(本州製紙株
式会社製)を、そして残りの1つには、前記本発明に係
る混合不織布の細片1gを入れた。なお、ビニール袋内
のエチレン発生を助長する目的で、上記の外に各袋内に
、既に腐敗の始まっているニラを1株宛入れて腐敗化を
促進させた。これらの試験試料は、いずれも15度C程
度の室温下に放置した。その結果、先ず同年12月9日
に至り、自然放置したものの葉に背比が起り、腐敗の始
まったことが確認された。次いで同年12月10日に至
り、グリーンパンクを入れたものに、また、同年12月
13日に至り活性炭を臭素酸塩−稀酸処理したものを入
れたものに、それぞれ葉の背比が始まった。これに対し
て本発明に係るものにおいては、更に7日間経過した1
2月20日にようやく葉の背比が始まった。
First, 5 kg of chives harvested on December 4, 1982 in Oita City were divided into 4 equal parts of 1.25 kg on December 6 of the same year.
The first group was left as it was, and the other three groups were each 25cm thick.
It was stored in a micron polyethylene film bag and sealed. One of them contained a 5g bag of Green Punk, a commercially available freshness preservation agent (composed of activated carbon and zeolite), and the other contained a bag containing commercially available activated carbon with bromate. - A 5 g bag (manufactured by Honshu Paper Industries Co., Ltd.) treated with a dilute acid system was placed in the bag, and 1 g of the mixed nonwoven fabric according to the present invention was placed in the remaining bag. In addition, in order to promote the generation of ethylene in the plastic bags, in addition to the above, one chive plant that had already started to rot was placed in each bag to promote rotting. These test samples were all left at room temperature of about 15 degrees Celsius. As a result, on December 9th of the same year, it was confirmed that the leaves, which had been left to grow naturally, began to curl, indicating the beginning of rot. Next, on December 10th of the same year, the leaves began to change in height, and on December 13th of the same year, the leaves began to change in height with activated carbon treated with bromate and dilute acid. Ta. On the other hand, in the case of the present invention, after 7 days have elapsed,
The leaves finally began to change their height on February 20th.

次に同様な手法で、ブロッコリーの鮮度保持効果を検討
した。
Next, we used a similar method to examine the effect of keeping broccoli fresh.

即ち、鳥取県中両町において昭和58年12月3日嵯取
穫したブロッコリー7.5kgを同年12月6日に4等
分し、ニラの場合と同様にしてそれぞれの鮮度保持能力
を、ブロッコリーの開花時期を目安にして判定した。但
し、ビニール袋中に同封する前出の市販の鮮度保持剤は
、ニラの場合と同様に5g入り袋をそれぞれ1個宛用い
たが、本発明に係る不織布については0.5gを用いた
。その結果、先ず自然放置のものは同年12月8日に、
また、グリーンバンク入りのものは同年12月10日に
、そして、活性炭を臭素酸塩−稀酸系で処理したものを
入れた7ηのは、同年12月12日に至ってそれぞれ開
花し始め、商品価値番失なった。これに対して本発明に
係るものは、同年12月25日に至ってようやく開花し
た。
That is, 7.5 kg of broccoli harvested on December 3, 1980 in Nakaryo-cho, Tottori Prefecture was divided into four equal parts on December 6 of the same year, and the freshness retention ability of each was determined in the same way as with chives. Judgment was made using the flowering time as a guide. However, as for the above-mentioned commercially available freshness-preserving agent enclosed in a plastic bag, one bag containing 5 g was used for each bag as in the case of chives, but 0.5 g was used for the nonwoven fabric according to the present invention. As a result, first of all, on December 8th of the same year,
In addition, the one containing Green Bank began to bloom on December 10th of the same year, and the 7η containing activated carbon treated with bromate-dilute acid system began flowering on December 12th of the same year. It has lost its value. In contrast, the plants according to the present invention finally bloomed on December 25th of the same year.

これらの例からして本発明に係るシートは、野菜の鮮度
保持に、従来品と比較して抜群の効果を発揮することが
明らかになった。
From these examples, it is clear that the sheet according to the present invention exhibits an outstanding effect in preserving the freshness of vegetables compared to conventional products.

〔実施例2〕 高結晶化度の繊維素繊維を出発原料とした活性炭素繊維
30パーセント、及び、フィブリル化した繊維素の短繊
維70パーセントからなる市販の活性炭素繊維KFペー
パー3g(厚さ250ミクロン、面積450平方センチ
メートル)を採り、これを臭素酸カリウム15重量パー
セントを含んだ0.5モルの補佐酸水溶液150ccに
10分間浸積し7た。投入前の水溶液の温度は40度C
であり、KFペーパー浸積直後より温度は急速に上昇し
始め、2分後には50度Cまで達した。脱水及び水洗を
3回繰り返し、反応残液の除去を行い、次いで105度
Cで乾燥して水分を除去した。また、この処理によって
出発原料のKFペーパーはより柔軟性を増し、被覆性の
向上が認められた。この処理ペーパーを用い15度C前
後の室温下におけるリンゴ、柿及びトマトの鮮度保持効
果を調べた。即ち、昭和58年12月1日、市販の長野
懸崖スターリンゴ、山梨懸崖富有柿及び愛知懸崖ファー
ストトマトそれぞれ6個を3等分し、その1群を自然放
置した。また、他の1群を、実施例Iで作製した不織布
1gとともにビニール袋内に密封した。そして、最後の
1群は、本実施例にて作製したKFペーパー処理のもの
を、当該果実等の上面を直接覆うように被せるだけにし
て、解放下に室温放置した。かくして2週間経過後の同
年12月14日に、鮮度保持の状態を観察した。先ず自
然放置のものは、トマト及び柿ともがくは緑色並びに柔
軟性を失い、果肉は軟化が進んで植物体を失なっていた
。また、リンゴは果面が一部褐色に変化するとともに、
柄が枯れていた。
[Example 2] 3 g of commercially available activated carbon fiber KF paper (thickness 250 micron, area 450 square centimeters) was taken and immersed for 10 minutes in 150 cc of a 0.5 molar auxiliary acid aqueous solution containing 15 weight percent of potassium bromate. The temperature of the aqueous solution before injection is 40 degrees C.
Immediately after the KF paper was immersed, the temperature began to rise rapidly and reached 50 degrees Celsius after 2 minutes. Dehydration and water washing were repeated three times to remove residual reaction liquid, and then drying was performed at 105° C. to remove water. Furthermore, this treatment made the starting material KF paper more flexible, and it was observed that the coating properties were improved. Using this treated paper, the effect of preserving the freshness of apples, persimmons, and tomatoes at room temperature around 15 degrees Celsius was investigated. That is, on December 1, 1981, six commercially available Nagano Kengai star apples, Yamanashi Kengai Fuyu persimmons, and Aichi Kengai first tomatoes were each divided into three equal parts, and one group was left to naturally grow. In addition, another group was sealed in a plastic bag together with 1 g of the nonwoven fabric produced in Example I. In the last group, the KF paper-treated fruit prepared in this example was simply placed on the upper surface of the fruit, etc., and left open at room temperature. Two weeks later, on December 14 of the same year, the state of freshness maintenance was observed. First, tomatoes and persimmons that were left to grow lost their green color and flexibility, and their pulps softened and lost their plant bodies. In addition, some of the fruit surfaces of apples turn brown, and
The handle was withered.

これに対して、本発明に係る混合不織布並びにKFペー
パー処理のものを用いたものは、両者ともトマト及び柿
について一部変色が見られたものの、保存状態は良好で
あって商品価値を失なうまでには至ってぃなかった。ま
た、リンゴの場合は完全な状態を維持し、柄も買入れ時
と変らなかった。
On the other hand, in the case of the mixed nonwoven fabric according to the present invention and the one treated with KF paper, although some discoloration was observed in tomatoes and persimmons, the preservation condition was good and the product value was not lost. I wasn't quite there yet. In addition, the apples remained in perfect condition and the handles were the same as when they were purchased.

以上のように本発明に係るものは、活性炭を基材とした
エチレン吸収能を有する鮮度保持剤と違って、果実全面
に渡って被覆可能なため、特に解放下であっても密閉時
の場合と略同等の鮮度保持効果を持つことが判明した。
As described above, unlike the freshness preserving agent which is based on activated carbon and has ethylene absorption ability, the product according to the present invention can cover the entire surface of the fruit, especially when it is open or closed. It was found that it has approximately the same freshness retention effect as

また、実施例1におけるブロッコリーの鮮度保持の比較
実験において、実施例2で作製したKFペーパー処理の
もの1.5g (含有炭素繊維0.5g)を実施例1の
混合不織布の代わりに用いた場合には、鮮度保持期間は
更に2週間程度延長され、略1カ月間の長期に渡り開花
を見ず、その鮮度が保持されることが確認された。これ
は、ペーパー内に多量に含有された繊維素IJll維の
水分吸収能による相乗効果によるものと考えられる。
In addition, in a comparative experiment of maintaining the freshness of broccoli in Example 1, when 1.5 g (containing carbon fiber 0.5 g) of the KF paper-treated fabric prepared in Example 2 was used instead of the mixed nonwoven fabric of Example 1. In this case, the freshness retention period was further extended by about two weeks, and it was confirmed that the freshness was maintained without blooming for a long period of about one month. This is thought to be due to the synergistic effect of the water absorbing ability of the cellulose IJll fibers contained in the paper in large amounts.

特許出願人 羽 1) 武 栄 手続゛補正書(方 式) 昭和60年3月8日 特許庁長官 志賀 学 殿 3、補正をする者 事件との関係 特許出願人 住 所 山梨県富士吉田市上吉田3814番地氏名 羽
田武栄 (名 称) 4、代理人 住 所 東京都中央区京橋1丁目14番5号土屋ビル5
階 (2)添付の通り委任状を補充する。
Patent Applicant Han 1) Takeei Procedures Written Amendment (Format) March 8, 1985 Manabu Shiga, Commissioner of the Patent Office 3 Relationship with the person making the amendment Patent Applicant Address Fujiyoshida City, Yamanashi Prefecture 3814 Yoshida Name: Takee Haneda (first name) 4, Agent address: 5 Tsuchiya Building, 1-14-5 Kyobashi, Chuo-ku, Tokyo
Floor (2) Supplement the power of attorney as attached.

Claims (1)

【特許請求の範囲】[Claims] 高結晶化度の繊維素繊維を炭化処理して得られる多孔質
の炭素繊維の短繊維に、臭素酸塩−稀酸水溶液処理を施
して得た炭素繊維と、フィブリル化した繊維素とからな
る果菜類の鮮度保持用シート。
Consists of carbon fibers obtained by subjecting short fibers of porous carbon fibers obtained by carbonizing high-crystallinity cellulose fibers to bromate-dilute acid aqueous solution treatment and fibrillated cellulose fibers. A sheet for preserving the freshness of fruits and vegetables.
JP59000144A 1984-01-04 1984-01-04 Sheet for preserving freshness of vegetables Granted JPS60176538A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP59000144A JPS60176538A (en) 1984-01-04 1984-01-04 Sheet for preserving freshness of vegetables

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP59000144A JPS60176538A (en) 1984-01-04 1984-01-04 Sheet for preserving freshness of vegetables

Publications (2)

Publication Number Publication Date
JPS60176538A true JPS60176538A (en) 1985-09-10
JPS6112651B2 JPS6112651B2 (en) 1986-04-09

Family

ID=11465826

Family Applications (1)

Application Number Title Priority Date Filing Date
JP59000144A Granted JPS60176538A (en) 1984-01-04 1984-01-04 Sheet for preserving freshness of vegetables

Country Status (1)

Country Link
JP (1) JPS60176538A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6356625U (en) * 1986-10-01 1988-04-15
JPS6432040U (en) * 1987-08-19 1989-02-28
JPH0282081A (en) * 1988-09-19 1990-03-22 Matsushita Refrig Co Ltd Vegetable chamber for refrigerator
JPH0494987U (en) * 1991-01-11 1992-08-18
CN104727187A (en) * 2015-02-06 2015-06-24 盐城工学院 Air-conditioning paper for grape preservation

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI86815C (en) * 1987-01-23 1992-10-26 Ok Vise Ky ROTATIONSPALETTSYSTEM

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6356625U (en) * 1986-10-01 1988-04-15
JPH0521406Y2 (en) * 1986-10-01 1993-06-01
JPS6432040U (en) * 1987-08-19 1989-02-28
JPH0282081A (en) * 1988-09-19 1990-03-22 Matsushita Refrig Co Ltd Vegetable chamber for refrigerator
JPH0494987U (en) * 1991-01-11 1992-08-18
CN104727187A (en) * 2015-02-06 2015-06-24 盐城工学院 Air-conditioning paper for grape preservation

Also Published As

Publication number Publication date
JPS6112651B2 (en) 1986-04-09

Similar Documents

Publication Publication Date Title
CN101601420B (en) Controlled-bactericide-release fruit and vegetable preservative packaging composite film, preparation method thereof, and use thereof
KR101158606B1 (en) Inhibition method of fruit softening
CN107261814B (en) High-efficiency ethylene absorbent for fruit and vegetable fresh-keeping and preparation method thereof
CN101176482B (en) Fabric nonwoven cloth fruit and vegetable preservative film series product
JPS60176538A (en) Sheet for preserving freshness of vegetables
CN110463754A (en) A kind of biology composite slow release type antistaling agent and preparation method
CN112495343A (en) Anti-mildew drying agent and preparation method thereof
CN107788106A (en) A kind of nonwoven fabric base composite fresh-keeping material and preparation method thereof
JPH02175140A (en) Film for preserving freshness of vegetable and fruit
CN107804049B (en) Preservative film and preparation method thereof
JPS61108359A (en) Preservation of food
KR20130012037A (en) Foaming compositions for fruits and vegetables
DE3590446T1 (en) Medium moisture vegetables
CN109679151A (en) Edible film, preparation method and application thereof
JPH0153020B2 (en)
Rathore et al. Effect of polyethylene packaging and coating having fungicide, ethylene absorbent and anti-ripening agent on the overall physicochemical composition of chaunsa white variety of mango at ambient temperature during storage
JP2000220225A (en) Antibacterial humidity conditioning panel and manufacture thereof
JP2917343B2 (en) How to keep fruits and vegetables fresh
Widayanti et al. Effect of activated nanostructured zeolite application on characteristics and postharvest life of chilli (Capsicum annuum L.)
CN107988796A (en) A kind of plastic fresh-keeping membrane and preparation method for Kiwi berry packaging
JPH024443A (en) Ethylene removing agent and freshness retaining method for vegetables and fruits using said ethylene removing agent
CN109315483A (en) A kind of fresh-ness preserving agent for vegetable and application thereof
JP4407806B2 (en) Method for inhibiting germination and rooting of garlic and package for ethylene generation
CN107747252B (en) Mildew-proof fresh-keeping coated paper and preparation method thereof
JPS627812B2 (en)