JP2018027063A - Freshness preservative of vegetable and fruit - Google Patents
Freshness preservative of vegetable and fruit Download PDFInfo
- Publication number
- JP2018027063A JP2018027063A JP2016161347A JP2016161347A JP2018027063A JP 2018027063 A JP2018027063 A JP 2018027063A JP 2016161347 A JP2016161347 A JP 2016161347A JP 2016161347 A JP2016161347 A JP 2016161347A JP 2018027063 A JP2018027063 A JP 2018027063A
- Authority
- JP
- Japan
- Prior art keywords
- freshness
- powder
- hypochlorous acid
- aqueous solution
- supported
- 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.)
- Pending
Links
Landscapes
- Carbon And Carbon Compounds (AREA)
- Storage Of Fruits Or Vegetables (AREA)
- Silicon Compounds (AREA)
Abstract
Description
本発明は、新規な鮮度保持剤に関する。詳しくは、次亜塩素酸水溶液を特定の条件で担持させた粉末を使用し、青果物の成熟メカニズムに作用するエチレン等の物質を分解すると共に、青果物の腐敗をもたらす真菌、細菌等を効果的に抑制することが可能な鮮度保持剤を提供するものである。 The present invention relates to a novel freshness-preserving agent. Specifically, using powder containing hypochlorous acid aqueous solution under specific conditions, it decomposes ethylene and other substances that affect the maturation mechanism of fruits and vegetables, and effectively prevents fungi, bacteria, etc. that cause fruits and vegetables to rot. A freshness-preserving agent that can be suppressed is provided.
近年、海外において日本食が人気を得ている。これに伴い海外での日本食材、特に青果物への関心が高くなり、需要が増してきている。これらの流通を実現するためは青果物の鮮度を保って、安価に輸送する技術が必要である。青果物の鮮度を維持するために短期間で輸送する方法としては、航空輸送が実施されているが輸送費が高い欠点がある。一方、コンテナに積載して海上輸送すれば、大量の青果物の輸送が可能で輸送費は低減できる。しかし、海上輸送は輸送日数がかかるために青果物の鮮度保持剤の性能向上、青果物の腐敗をもたらす真菌、細菌等を抑制する従来以上の技術が求められる。 In recent years, Japanese food has gained popularity overseas. Along with this, interest in Japanese foods overseas, especially fruits and vegetables, has increased and demand has increased. In order to realize such distribution, it is necessary to maintain the freshness of fruits and vegetables and transport them at low cost. As a method of transporting fruits and vegetables in a short period of time to maintain the freshness of the fruits and vegetables, air transportation is carried out, but there is a drawback that transportation costs are high. On the other hand, if the container is loaded on the sea, a large amount of fruits and vegetables can be transported and the transportation cost can be reduced. However, since marine transportation takes many days of transportation, there is a need for more than conventional techniques to improve the performance of freshness-preserving agents for fruits and vegetables, and to suppress fungi, bacteria, etc. that cause the fruits to decay.
青果物の鮮度保持剤としては、現在、各種のものが市販されている。その例としては、活性炭、活性炭に臭素系酸化剤を添加したもの、活性炭に塩化パラジウムを添加したもの、天然ゼオライトに過マンガン酸カリウムを添加したもの等があるが、鮮度保持性能において未だ改善の余地がある。 Various kinds of freshness-preserving agents for fruits and vegetables are currently commercially available. Examples include activated carbon, activated carbon with bromine oxidant added, activated carbon with palladium chloride added, natural zeolite with potassium permanganate added, etc. There is room.
一方、青果物の成熟メカニズムに作用するエチレン等の物質を分解するとともに、青果物の腐敗をもたらす真菌、細菌等を抑制する鮮度保持剤として、次亜塩素酸塩が注目されており、例えば、次亜塩素酸塩と多孔質粒子を組み合わせるものが提案されている(特許文献1、2参照)。 On the other hand, hypochlorite is attracting attention as a freshness-preserving agent that decomposes substances such as ethylene that act on the maturation mechanism of fruits and vegetables, and suppresses fungi, bacteria, etc. that cause the decay of fruits and vegetables. A combination of chlorate and porous particles has been proposed (see Patent Documents 1 and 2).
しかしながら、上記鮮度保持剤は、多孔質粒子の特性について全く検討が成されておらず、次亜塩素酸塩の性能を十分発揮し得ているものとは言えない。 However, the freshness-keeping agent has not been studied at all with respect to the characteristics of the porous particles, and it cannot be said that the performance of hypochlorite can be sufficiently exhibited.
例えば、特許文献1では、具体的に示されている鮮度保持剤は天然ゼオライトと次亜塩素酸カルシウム粉末の混合物であり、天然ゼオライトによる吸着効果は期待されるものの、次亜塩素酸塩の効果は単体で使用した場合と効果は変わるものではない。 For example, in Patent Document 1, the freshness-keeping agent specifically shown is a mixture of natural zeolite and calcium hypochlorite powder, and although the adsorption effect by natural zeolite is expected, the effect of hypochlorite The effect does not change when used alone.
また、特許文献2においては、次亜塩素酸塩の効果を引き出そうとするあまり、多孔質粒子に対して多量の次亜塩素塩水溶液を使用しており、次亜塩素酸水溶液が多孔質粒子表面を覆い、かかる表面に存在する次亜塩素酸水溶液を単体で使用した場合と効果は変わるものではない。 Further, in Patent Document 2, a large amount of hypochlorite aqueous solution is used for the porous particles because of the excessive effect of hypochlorite, and the hypochlorous acid aqueous solution is the surface of the porous particles. The effect is not different from the case where the hypochlorous acid aqueous solution present on the surface is used alone.
更に、pH9〜14に調整した亜塩素酸水溶液を多孔質無機担体に含侵させることにより二酸化塩素ガス生成物を発生される方法が開示されている(特許文献3)。しかし、二酸化塩素ガスを発生させる方法はその発生量をコントロールすることが難しい。しかも、二酸化塩素ガスの多量の発生は、使用環境に与える影響が懸念される。 Furthermore, a method is disclosed in which a chlorine dioxide gas product is generated by impregnating a porous inorganic carrier with an aqueous solution of chlorous acid adjusted to pH 9 to 14 (Patent Document 3). However, it is difficult to control the amount of chlorine dioxide gas generated by the method. Moreover, the generation of a large amount of chlorine dioxide gas is concerned about the influence on the use environment.
従って、本発明の目的は、多孔質粒子と次亜塩素酸水溶液とを組合せた鮮度保持剤において、高い鮮度保持の効果を有すると共に、二酸化塩素ガスの発生量が少なく、使用環境への影響が少ない鮮度保持剤を提供することにある。 Accordingly, an object of the present invention is to provide a freshness-keeping agent that combines porous particles and a hypochlorous acid aqueous solution, has a high freshness-keeping effect, produces a small amount of chlorine dioxide gas, and has no influence on the use environment. It is to provide a low freshness-preserving agent.
本発明者らは、上記問題点を解決すべく鋭意検討を重ねた。その結果、特定の多孔質シリカ粉末を用いて、多孔質シリカ粉末に次亜塩素酸水溶液を特定の割合で担持させることにより、従来の担持型の鮮度保持剤に比べて高い鮮度保持効果を発揮すると共に、次亜塩素酸塩のもつ真菌、細菌等を抑制する能力をも最大限に発揮し得ること、更には、剤からの二酸化塩素ガス等の有効成分の発生量も極めて少ないことから、環境に優しい鮮度保持剤が得られることを見出し、本発明を完成するに至った。 The present inventors have intensively studied to solve the above problems. As a result, by using a specific porous silica powder and supporting a hypochlorous acid aqueous solution at a specific ratio on the porous silica powder, a high freshness retention effect is exhibited compared to a conventional supported freshness-keeping agent. In addition, the ability to suppress fungi, bacteria, etc. possessed by hypochlorite can be maximized, and furthermore, the amount of active ingredients such as chlorine dioxide gas generated from the agent is extremely small, The inventors have found that an environmentally friendly freshness-keeping agent can be obtained, and have completed the present invention.
即ち、本発明によれば、全細孔容積0.3〜2.5cc/g、該全細孔容積において細孔直径70〜1000オングストロームの細孔が80%以上を占める細孔を有し、平均粒子径が200〜2000μmの多孔質シリカ粉末に、次亜塩素酸水溶液を、該多孔質シリカ粉末の該全細孔容積の80%以下で、且つ、該多孔質シリカ粉末100質量部に対して有効塩素が0.02〜40質量部となるように担持させた次亜塩素酸水溶液担持粉末を含むことを特徴とする鮮度保持剤が提供される。 That is, according to the present invention, the total pore volume is 0.3 to 2.5 cc / g, and the total pore volume has pores with a pore diameter of 70 to 1000 angstroms occupying 80% or more, An aqueous solution of hypochlorous acid is added to a porous silica powder having an average particle size of 200 to 2000 μm at 80% or less of the total pore volume of the porous silica powder and 100 parts by mass of the porous silica powder. Thus, a freshness-keeping agent is provided, comprising a hypochlorous acid aqueous solution-supported powder supported so that the effective chlorine content is 0.02 to 40 parts by mass.
前記のような次亜塩素酸水溶液担持粉末は、前記のように次亜塩素酸水溶液の担持量を調整することにより、安息角が60度以下という高い流動性を示す。 The above-mentioned hypochlorous acid aqueous solution-supported powder exhibits high fluidity with an angle of repose of 60 degrees or less by adjusting the amount of hypochlorous acid aqueous solution supported as described above.
また、前記使用する多孔質シリカ粉末は、ゲル法シリカ粉末または沈降法シリカ粉末が好適である。 The porous silica powder to be used is preferably a gel method silica powder or a precipitation method silica powder.
更に、本発明の鮮度保持剤は、平均細孔径が10〜30オングストローム、比表面積が700〜1500m2/g、平均粒子径が100〜10000μmの活性炭粉末を併用することが好ましく、その使用量は、前記次亜塩素酸水溶液担持粉末100質量部に対して0.1〜500質量部の割合が好ましい。
また、本発明の鮮度保持剤は、通気性袋に充填して使用することが取扱上好ましい。
Furthermore, the freshness-keeping agent of the present invention is preferably used in combination with activated carbon powder having an average pore diameter of 10 to 30 angstroms, a specific surface area of 700 to 1500 m 2 / g, and an average particle diameter of 100 to 10,000 μm. A ratio of 0.1 to 500 parts by mass with respect to 100 parts by mass of the hypochlorous acid aqueous solution-supported powder is preferable.
Moreover, it is preferable on handling that the freshness-keeping agent of the present invention is filled in a breathable bag.
本発明の鮮度保持剤は、前記特定の担体に、前記特定量の次亜塩素酸水溶液を担持させることにより、二酸化塩素ガスの発生量を極めて少なく抑えながらも、青果物の成熟メカニズムに作用するエチレン等の物質の分解効果、及び、青果物の腐敗をもたらす真菌、細菌等の抑制効果(以下、これらを「鮮度保持効果」ともいう)が極めて高いという特徴を有する。 The freshness-preserving agent of the present invention is an ethylene that acts on the maturation mechanism of fruits and vegetables while supporting the specific amount of hypochlorous acid aqueous solution on the specific carrier, while suppressing the generation amount of chlorine dioxide gas extremely low. And the like, and the suppression effect of fungi, bacteria, etc. that cause the decay of fruits and vegetables (hereinafter also referred to as “freshness retention effect”) is extremely high.
また、前記特定の微粉活性炭造粒体を併用した本発明の鮮度保持剤は、二酸化塩素ガスの発生量をより抑えながら、それぞれを単独で使用した場合に比べて、高い鮮度保持効果を発揮することが可能である。 In addition, the freshness-keeping agent of the present invention combined with the specific fine powder activated carbon granule exhibits a higher freshness-keeping effect as compared with the case where each is used alone while suppressing the generation amount of chlorine dioxide gas. It is possible.
従って、本発明の鮮度保持剤は、使用環境への影響をほとんど与えず、それでいながら、優れた鮮度保持効果を有する鮮度保持剤を提供することができる。 Therefore, the freshness-keeping agent of the present invention hardly gives an influence on the use environment, and can still provide a freshness-keeping agent having an excellent freshness-keeping effect.
本発明の鮮度保持剤において、次亜担持粉が前記した鮮度保持効果を発揮する機構は明らかではないが、本発明者らは、かかる機構を次のように推定している。 In the freshness-keeping agent of the present invention, the mechanism by which the hypoxia-supported powder exhibits the above-described freshness-keeping effect is not clear, but the present inventors presume this mechanism as follows.
即ち、次亜塩素酸水溶液を担持した多孔質シリカ粉末の粒子は、表面近傍の細孔では次亜塩素酸水溶液が存在しない細孔空間を有し、かかる細孔空間内に拡散してきたエチレンは、細孔内に存在するシラノール基の作用により活性化された次亜塩素酸水溶液との接触により、また、上記細孔空間に存在する二酸化塩素との接触により、効果的に分解するものと推定している。また、多孔質シリカ粉末の細孔内に存在するシラノール基の作用により、担持した次亜塩素酸水溶液が局所的に弱酸性次亜塩素酸となることにより、青果物の腐敗をもたらす真菌、細菌等の細菌に対してもこれを抑制する効果を発揮する。 That is, the porous silica powder particles carrying the hypochlorous acid aqueous solution have a pore space where the hypochlorous acid aqueous solution does not exist in the pores near the surface, and the ethylene diffused in the pore space is It is estimated that it is effectively decomposed by contact with a hypochlorous acid aqueous solution activated by the action of silanol groups present in the pores and by contact with chlorine dioxide existing in the pore space. doing. Also, fungi, bacteria, etc. that cause spoilage of fruits and vegetables when the supported hypochlorous acid aqueous solution becomes weakly acidic hypochlorous acid locally by the action of silanol groups present in the pores of the porous silica powder. It also has the effect of suppressing this against bacteria.
以下、本発明の方法について詳細に説明する。 Hereinafter, the method of the present invention will be described in detail.
本発明の鮮度保持剤は、多孔質シリカ粉末に対して、次亜塩素酸水溶液を担持させた次亜塩素酸水溶液担持粉末(以下、「次亜担持粉末」ともいう。)を主体とする。 The freshness-keeping agent of the present invention is mainly composed of a hypochlorous acid aqueous solution-supported powder (hereinafter also referred to as “hypochlorous powder”) in which a hypochlorous acid aqueous solution is supported on a porous silica powder.
上記多孔質シリカ粉末は、全細孔容積0.3〜2.5cc/g、好ましくは、0.5〜2.0cc/g、該全細孔容積において細孔直径70〜1000オングストロームの細孔が80%以上、好ましくは、70%以上を占める細孔を有し、平均粒子径200〜2000μm、好ましくは、500〜1800μmのものが、次亜塩素酸水溶液を担持させる粉末として有効である。ここで言う全細孔容積、細孔直径は窒素吸着法により測定したものである。 The porous silica powder has a total pore volume of 0.3 to 2.5 cc / g, preferably 0.5 to 2.0 cc / g, and a pore diameter of 70 to 1000 angstroms in the total pore volume. Having a pore occupying 80% or more, preferably 70% or more, and having an average particle size of 200 to 2000 μm, preferably 500 to 1800 μm, is effective as a powder for supporting a hypochlorous acid aqueous solution. The total pore volume and the pore diameter mentioned here are measured by a nitrogen adsorption method.
即ち、上記全細孔容積は、次亜担持粉末における次亜塩素酸水溶液の担持量を決定するものであり、前記範囲より少ない場合は、次亜塩素酸水溶液の担持量を十分確保できず、鮮度保持効果が短時間で低減する。また、全細孔容積が前記範囲より多い場合、混合する次亜塩素酸が不均一な分布になりやすく、鮮度保持剤としての効果にばらつきが生じる。 That is, the total pore volume is to determine the amount of hypochlorous acid aqueous solution supported in the hypochlorous powder, if less than the above range, it is not possible to ensure a sufficient amount of hypochlorous acid aqueous solution, The effect of maintaining freshness is reduced in a short time. Further, when the total pore volume is larger than the above range, the hypochlorous acid to be mixed tends to have a non-uniform distribution, and the effect as a freshness maintaining agent varies.
また、前記多孔質シリカ粉末において、細孔直径70〜1000オングストロームの細孔は、次亜塩素酸水溶液を担持するために好適な大きさの細孔であり、かかる大きさの細孔が占める割合が80%より少ない場合は、細孔直径が小さいもの、大きいものが多く存在することになり、混合した次亜塩素酸の気相への存在割合が小さくなり、鮮度保持剤としての効果が小さくなる等の問題が生じる。 Further, in the porous silica powder, pores having a pore diameter of 70 to 1000 angstroms are pores having a size suitable for supporting a hypochlorous acid aqueous solution, and a ratio of the pores having such a size is occupied. Is less than 80%, there are many small and large pore diameters, the proportion of mixed hypochlorous acid in the gas phase is small, and the effect as a freshness-preserving agent is small. The problem of becoming.
更に、前記多孔質シリカの平均粒子径が、200μmより小さい場合は、粉立ちが起こり易く、取扱において問題となる。また、該平均粒子径が2000μmを超える場合は、鮮度保持剤としての性能にばらつきが生じやすくなる。 Furthermore, when the average particle diameter of the porous silica is smaller than 200 μm, powdering tends to occur, which causes a problem in handling. Moreover, when this average particle diameter exceeds 2000 micrometers, it will become easy to produce dispersion | variation in the performance as a freshness keeping agent.
上記多孔質シリカ粉末としては、湿式シリカ粉末に分類されるものが前記条件を満足する上で好適である。かかる湿式シリカ粉末は、ゲル法シリカまたは沈降法シリカが好適であり、上記ゲル法シリカはケイ酸ナトリウムと鉱酸の反応を酸性領域で行うことで、ゲル状の塊をつくり、これを乾燥させて製造する方法であり、また、沈降法シリカはケイ酸ナトリウムと鉱酸の反応をアルカリ領域で凝集沈降させて製造する方法である。 As the porous silica powder, those classified as wet silica powder are suitable for satisfying the above conditions. The wet silica powder is preferably gel method silica or precipitation method silica, and the gel method silica forms a gel-like lump by performing a reaction between sodium silicate and mineral acid in an acidic region, which is dried. The precipitated silica is produced by agglomerating and precipitating the reaction of sodium silicate and mineral acid in the alkaline region.
本発明の鮮度保持剤において、前記多孔質シリカ粉末への次亜塩素酸水溶液の担持量は、多孔質シリカ粉末の全細孔容積の80%以下、好ましくは、70%以下とすることが必要である。即ち、多孔質シリカ粉末に対して次亜塩素水溶液を全細孔容積の80%を超えて担持させた場合、次亜塩素酸水溶液が多孔質シリカ粉末を構成する粒子の表面に滲出し、かかる次亜塩素酸水溶液は、大気に大量の二酸化塩素を放出し、青果物への臭気の移行や、周囲の環境にも悪影響を与えるばかりでなく、粒子表面がべた付くことにより、粒子同士の凝集が起こり易く取扱性が低下するという問題をも有する。 In the freshness-keeping agent of the present invention, the amount of hypochlorous acid aqueous solution supported on the porous silica powder needs to be 80% or less, preferably 70% or less, of the total pore volume of the porous silica powder. It is. That is, when a hypochlorous acid aqueous solution is supported on the porous silica powder exceeding 80% of the total pore volume, the hypochlorous acid aqueous solution exudes to the surface of the particles constituting the porous silica powder. Aqueous hypochlorous acid releases a large amount of chlorine dioxide into the atmosphere, which not only transfers odors to fruits and vegetables, but also adversely affects the surrounding environment. It also has the problem that it is easy to occur and handling property falls.
尚、前記多孔質シリカ粉末への次亜塩素酸水溶液の担持量の下限は、鮮度保持効果が発揮される範囲であれば特に制限されないが、20%、特に、40%が好ましい。 The lower limit of the amount of the hypochlorous acid aqueous solution supported on the porous silica powder is not particularly limited as long as the freshness maintaining effect is exhibited, but is preferably 20%, particularly 40%.
本発明の鮮度保持剤を構成する次亜担持粉末は、多孔質シリカ粉末に対して次亜塩素水溶液を全細孔容積の80%以下とすることにより、粒子表面への次亜塩素酸水溶液の滲出が抑制されるため、高い流動性を示し、その安息角は60度以下を示す。そのため、包装材、容器等への充填、後述する微粉活性炭造粒体等を併用する場合、取り扱い、混合等の操作が容易であるという利点もある。 The hypochlorous support powder constituting the freshness-keeping agent of the present invention is a solution of hypochlorous acid aqueous solution on the particle surface by making the hypochlorous acid aqueous solution 80% or less of the total pore volume with respect to the porous silica powder. Since exudation is suppressed, high fluidity is exhibited, and the angle of repose is 60 degrees or less. Therefore, when filling a packaging material, a container, etc., and the fine powder activated carbon granule mentioned later are used together, there is also an advantage that operations such as handling and mixing are easy.
上記次亜担持粉末の次亜塩素酸水溶液を80%以下に調整する方法は特に制限されないが、好適な方法を例示すれば、多孔質シリカ粉末の前記全細孔容積を事前に測定し、該全細孔容積に対して80%以下となる量の次亜塩素酸水溶液を混合する方法が挙げられる。この場合、上記多孔質シリカ粉末と次亜塩素酸水溶液との混合は、多孔質シリカ粉末を撹拌しながら、必要量の次亜塩素酸水溶液をスプレーして担持する方法が、次亜塩素水水溶液を均一に担持せしめた次亜担持粉末を得るために有効である。 The method for adjusting the hypochlorous acid aqueous solution of the hypoxia-supported powder to 80% or less is not particularly limited, but if a suitable method is exemplified, the total pore volume of the porous silica powder is measured in advance, The method of mixing the hypochlorous acid aqueous solution of the quantity used as 80% or less with respect to the total pore volume is mentioned. In this case, the mixing of the porous silica powder and the hypochlorous acid aqueous solution is performed by spraying and supporting the required amount of the hypochlorous acid aqueous solution while stirring the porous silica powder. It is effective to obtain a hypo-supported powder in which is uniformly supported.
本発明の次亜担持粉末は、上記次亜塩素酸水溶液の担持量を特徴とすると共に、該次亜塩素酸水溶液を前記多孔質シリカ粉末100質量部に対して有効塩素が0.02〜40質量部、好ましくは、0.03〜35質量部、更に好ましくは、0.03〜10質量部となるように担持させることが重要である。 The hypochlorous acid support powder of the present invention is characterized by the amount of the hypochlorous acid aqueous solution supported, and the hypochlorous acid aqueous solution has an effective chlorine content of 0.02 to 40 parts per 100 parts by mass of the porous silica powder. It is important to carry it so that it may become a mass part, Preferably it is 0.03-35 mass part, More preferably, it is 0.03-10 mass part.
即ち、前記有効塩素量が0.02質量部未満であると、十分な鮮度保持効果が発揮されず、また、40質量部を超えても効果が頭打ちとなるばかりでなく、前記次亜塩素酸水溶液の担持量を勘案すれば、使用する次亜塩素酸水溶液の濃度を上げる必要があり、次亜塩素酸水溶液の分解が大きくなる等の問題が生じる虞がある。 That is, when the effective chlorine amount is less than 0.02 parts by mass, a sufficient freshness maintaining effect is not exhibited, and when the amount exceeds 40 parts by mass, the effect reaches a peak, and the hypochlorous acid is not limited. Considering the amount of aqueous solution supported, it is necessary to increase the concentration of the hypochlorous acid aqueous solution to be used, and there is a possibility that problems such as an increase in decomposition of the hypochlorous acid aqueous solution may occur.
尚、次亜担持粉末に担持された有効塩素濃度の測定は、後述の実施例において詳細に説明するが、次亜担持粉末を水に分散せしめて次亜塩素酸を水に溶解させ、溶解した水について通常の有効塩素濃度を測定する分析方法を用いて測定可能である。 Incidentally, the measurement of the effective chlorine concentration supported on the hypochlorous powder will be described in detail in Examples below, but the hypochlorous acid was dissolved in water by dispersing the hypochlorous powder in water and dissolved. It can be measured using an analytical method that measures the normal effective chlorine concentration for water.
本発明の鮮度保持剤において使用する次亜塩素酸水溶液の濃度は、前記次亜担持粉末における次亜塩素酸水溶液の担持量、有効塩素量を満足するのに好適な濃度を適宜選択すればよい。一般には、有効塩素濃度0.1〜20質量%、好ましくは、0.2〜18質量%のものが使用される。 The concentration of the hypochlorous acid aqueous solution used in the freshness-keeping agent of the present invention may be appropriately selected as a concentration suitable for satisfying the amount of hypochlorous acid aqueous solution supported and the amount of effective chlorine in the hypochlorous acid supported powder. . Generally, an effective chlorine concentration of 0.1 to 20% by mass, preferably 0.2 to 18% by mass is used.
尚、次亜塩素酸水溶液の有効塩素濃度は、単位溶液重量中に存在する有効塩素の重量で定義される。一般的にはヨウ化カリウムを用いた酸化還元反応により、遊離したヨウ素を滴定することで求められる。溶液中の1モルの次亜塩素酸ナトリウムが存在すれば、1モルの有効塩素に相当する。 The effective chlorine concentration of the hypochlorous acid aqueous solution is defined by the weight of effective chlorine present in the unit solution weight. Generally, it is determined by titrating free iodine by an oxidation-reduction reaction using potassium iodide. If 1 mol of sodium hypochlorite in solution is present, it corresponds to 1 mol of available chlorine.
また、前記次亜塩素酸水溶液は次亜塩素酸を含む水溶液であればよく、一般的には、次亜塩素酸ナトリウム、次亜塩素酸カリウム、次亜塩素酸カルシウム等の次亜塩素酸塩が単独または混合して使用される。 The aqueous hypochlorous acid solution may be an aqueous solution containing hypochlorous acid, and generally hypochlorite such as sodium hypochlorite, potassium hypochlorite, calcium hypochlorite and the like. Are used alone or in combination.
本発明の鮮度保持剤は、前記次亜担持粉末に対して、活性炭粉末を併用することにより、鮮度保持効果を一層向上することができる。その作用は明確ではないが、次亜担持粉末から微量発生するガス中に存在する二酸化塩素の如き有効性成分の一部を活性炭粉末が吸着することにより、活性炭粉末内部にも、有効成分の作用するサイトが形成され、活性炭による単なる吸着以上の鮮度保持効果が発揮されると共に、次亜担持粉末だけで除去できない微量成分等を活性炭が吸着することによる効果も発揮されるものと推定している。 The freshness-keeping agent of the present invention can further improve the freshness-keeping effect by using activated carbon powder in combination with the hypoxia-supported powder. Although the action is not clear, the activated carbon powder adsorbs a part of the active ingredient such as chlorine dioxide present in the gas generated in a small amount from the hypoxia-supported powder. It is presumed that the effect of the activated carbon adsorbing trace components that cannot be removed only by the hypoxia-supported powder is demonstrated, as well as the effect of maintaining the freshness beyond the simple adsorption by activated carbon. .
上記活性炭粉末は特に制限されるものではないが、平均細孔径が10〜30オングストローム、比表面積が700〜1500m2/g、平均粒子径が100〜10000μmの性状を有するものが好適に使用される。上記特性を有する活性炭粉末は、活性炭を50μm以下に微粉砕した後に、公知の方法により上記平均粒子径の大きさに造粒したものが好適に使用される。 The activated carbon powder is not particularly limited, but those having properties having an average pore diameter of 10 to 30 angstroms, a specific surface area of 700 to 1500 m 2 / g, and an average particle diameter of 100 to 10,000 μm are preferably used. . As the activated carbon powder having the above characteristics, activated carbon is pulverized to 50 μm or less and then granulated to the average particle size by a known method.
前記活性炭粉末の量は、次亜担持粉末100質量部に対して、0.1〜500質量部、特に0.2〜400質量部であることが併用による鮮度保持効果を十分発揮するために好ましい。 The amount of the activated carbon powder is preferably 0.1 to 500 parts by mass, particularly preferably 0.2 to 400 parts by mass with respect to 100 parts by mass of the hypoxia-supported powder in order to sufficiently exhibit the freshness maintaining effect by the combined use. .
また、本発明の鮮度保持剤は、青果物の鮮度保持剤として使用する場合、粉末であるが故に、青果物と直接触れるとその一部が青果物表面に残留することがあるため、不織布等の通気性袋に充填して使用することが好適な態様として挙げられる。一袋あたりの充填量は特に制限されないが、1g〜1kg、特に、5〜200g程度が実用的である。 In addition, since the freshness-preserving agent of the present invention is a powder when used as a freshness-preserving agent for fruits and vegetables, a part thereof may remain on the surface of fruits and vegetables when directly touched with fruits and vegetables. A preferred embodiment is to fill the bag for use. The amount of filling per bag is not particularly limited, but 1 g to 1 kg, particularly about 5 to 200 g is practical.
更に、本発明の鮮度保持剤を、上記通気性袋に充填して使用するに際し、青果物を詰めた包装用段ボール箱、コンテナ等の収容容器内に、かかる充填袋を適量、具体的には、次亜担持粉末が100〜2000g/m3、好ましくは、200〜1000g/m3となるように存在させることが好ましい。また、収容容器内における存在のさせ方も限定されるものではないが、例えば、包装用段ボール箱においては、充填袋をその内壁に貼着する態様、青果物間に介在させる態様が好ましく、コンテナにおいては、上記包装用段ボール箱を積載してもよいし、ばら積みの場合は、コンテナ内壁に前記充填袋を貼着したり、青果物間に介在させたりすることもできる。 Furthermore, when the freshness-preserving agent of the present invention is used by filling the breathable bag, an appropriate amount of the filling bag is contained in a container such as a packaging cardboard box or container filled with fruits and vegetables, specifically, It is preferable that the hypo-supported powder be present so as to be 100 to 2000 g / m 3 , preferably 200 to 1000 g / m 3 . In addition, although the manner of existence in the storage container is not limited, for example, in a cardboard box for packaging, a mode in which a filling bag is attached to the inner wall, a mode in which it is interposed between fruits and vegetables is preferable. The above-mentioned packaging cardboard boxes may be loaded, and in the case of bulk stacking, the filling bag may be stuck on the inner wall of the container or interposed between the fruits and vegetables.
以下、実施例を示して本発明を更に具体的に説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
尚、実施例において各測定値は以下の方法によって測定した。 In the examples, each measured value was measured by the following method.
1)次亜担持粉末の有効塩素量
次亜担持粉末10gを60ccの水に分散せしめて次亜塩素酸を水に溶解させた後、溶解した水に、ヨウ化カリウム、酢酸を加えて、次亜塩素酸と反応して溶出したヨウ素を0.01Nのチオ硫酸ナトリウム水溶液で滴定して有効塩素濃度を測定し、かかる測定値より、多孔質シリカ粉末100質量部に対する有効塩素量を算出した。
1) Effective chlorine content of hypochlorous powder After 10 g of hypochlorous powder was dispersed in 60 cc of water and hypochlorous acid was dissolved in water, potassium iodide and acetic acid were added to the dissolved water. The effective chlorine concentration was measured by titrating iodine eluted after reacting with chlorous acid with a 0.01N sodium thiosulfate aqueous solution, and the effective chlorine amount relative to 100 parts by mass of the porous silica powder was calculated from the measured value.
2)多孔質シリカ粉末に対する次亜塩素酸水溶液の担持割合
次亜担持粉末10gを真空乾燥に設置し、温度100℃、圧力10kPaで10時間乾燥し、重量を測定して容積換算した。真空乾燥によって減少した重量が多孔質シリカの細孔内に存在する次亜塩素酸水溶液の量であり、予め測定した多孔質シリカの全細孔容積で除して求めた。
2) Loading ratio of hypochlorous acid aqueous solution with respect to porous silica powder 10 g of hypochlorous acid supported powder was placed in vacuum drying, dried at a temperature of 100 ° C. and a pressure of 10 kPa for 10 hours, measured for weight, and converted into a volume. The weight reduced by vacuum drying is the amount of hypochlorous acid aqueous solution present in the pores of the porous silica, and is obtained by dividing by the total pore volume of the porous silica measured in advance.
3)多孔質シリカ粉末の全細孔容積、平均細孔直径
マイクロトラック・ベル株式会社製のBELSORP−mini(商品名)を用いて、窒素吸着により測定した。
3) Total pore volume and average pore diameter of porous silica powder Measured by nitrogen adsorption using BELSORP-mini (trade name) manufactured by Microtrack Bell Co., Ltd.
4)多孔質シリカの平均粒径
堀場製作所製のレーザ回折散乱式粒子径分布装置LA−950V2(商品名)を用いて測定した。
4) Average particle diameter of porous silica It measured using the laser diffraction scattering type particle size distribution apparatus LA-950V2 (brand name) by Horiba.
実施例1
多孔質シリカ粉末として、全細孔容積が1.2cc/g、平均細孔直径が173オングストローム、細孔直径70〜1000オングストロームの細孔は99%、平均粒子径が150μmの富士シリシア化学株式会社製のシリカゲルQ−10を3g採取して、有効塩素濃度10質量%の次亜塩素酸ナトリウム溶液0.1gを噴霧しながら撹拌混合したて担持させた。得られた次亜担持粉末の多孔質シリカ粉末に対する次亜塩素酸水溶液の担持量は、3.3%であった。また、有効塩素量は、0.3質量部/(100質量部−多孔質シリカ粒子)であった。
Example 1
As a porous silica powder, Fuji Silysia Chemical Co., Ltd. has a total pore volume of 1.2 cc / g, an average pore diameter of 173 angstrom, a pore diameter of 70 to 1000 angstrom, 99% of pores and an average particle diameter of 150 μm. 3 g of silica gel Q-10 produced was sampled and mixed with 0.1 g of sodium hypochlorite solution having an effective chlorine concentration of 10% by mass while stirring and supported. The amount of the hypochlorous acid aqueous solution supported on the porous silica powder of the obtained hypochlorous supported powder was 3.3%. Moreover, the amount of effective chlorine was 0.3 mass part / (100 mass part-porous silica particle).
その後、シリカゲルを混合して均一に混合した。こうして作成した次亜担持粉末の安息角は40度であった。得られた次亜担持粉末を単独で使用して鮮度保持剤とした。 Thereafter, silica gel was mixed and mixed uniformly. The repose angle of the hypo-supported powder thus prepared was 40 degrees. The obtained hypoxia-supported powder was used alone as a freshness-keeping agent.
次いで、この該鮮度保持剤3gを目皿上に入れ、内容積5リットルのデシケーターに200gの柿3個ともに入れ、室温で17日間放置した。17日後のデシケーター内のエチレンは検出されず、熟成も進まず、カビの発生もなかった。また、塩素臭は、殆ど無かった。 Next, 3 g of the freshness-keeping agent was put on a dish and put together with three 200 g baskets in a desiccator having an internal volume of 5 liters, and left at room temperature for 17 days. Ethylene in the desiccator after 17 days was not detected, ripening did not proceed, and no mold was generated. Moreover, there was almost no chlorine smell.
比較例1
ブランクの実験として、次亜担持粉末を用いない以外は実施例1の鮮度保持の実験と同様に行った。17日後のデシケーター内のエチレンは0.2ppm検出され、柿の熟成が進むとともに、カビの発生が確認された。
Comparative Example 1
The blank experiment was performed in the same manner as the experiment for maintaining the freshness of Example 1 except that hypochlorous support powder was not used. After 17 days, 0.2 ppm of ethylene in the desiccator was detected, and as ripening progressed, generation of mold was confirmed.
比較例2
有効塩素濃度10質量%の次亜塩素酸ナトリウム溶液8gを担持させた以外は実施例1とほぼ同様に次亜担持粉末を作成した。得られた次亜担持粉末の多孔質シリカ粉末に対する次亜塩素酸水溶液の担持量は、276%であった。また、有効塩素量は、53質量部/(100質量部−多孔質シリカ粒子)であった。また、こうして作成した次亜担持粉末は、表面が濡れており、その安息角は60度を遙かに超える大きい値を示した。また、17日後のデシケーター内のエチレンは0.2ppm検出され、柿の熟成は進んだが、カビの発生は確認されなかった。また、強い塩素臭があった。
Comparative Example 2
A hypoxia-supported powder was prepared in substantially the same manner as in Example 1 except that 8 g of a sodium hypochlorite solution having an effective chlorine concentration of 10% by mass was supported. The amount of hypochlorous acid aqueous solution supported on the porous silica powder of the obtained hypochlorous supported powder was 276%. Moreover, the effective chlorine amount was 53 mass parts / (100 mass parts-porous silica particle). The hypo-supported powder thus prepared had a wet surface, and the angle of repose showed a large value far exceeding 60 degrees. Further, 0.2 ppm of ethylene in the desiccator after 17 days was detected, and the ripening of the koji progressed, but generation of mold was not confirmed. There was also a strong chlorine odor.
実施例2
対象とする青果物を柿から苺に変更した以外は実施例1と同様に行った。デシケーターに苺を入れ室温で14日間放置した。14日後のデシケーター内のエチレンは検出されず、熟成もほとんど進まず、カビの発生もなかった。
Example 2
The same procedure as in Example 1 was performed except that the target fruits and vegetables were changed from strawberries to strawberries. A desiccator was placed in a bowl and left at room temperature for 14 days. Ethylene in the desiccator after 14 days was not detected, ripening hardly progressed, and no mold was generated.
実施例3
実施例2の次亜担持担体に、マイクロトラック・ベル株式会社製のBELSORP−miniを用いて、窒素吸着により測定した平均細孔径が22オングストローム、比表面積が923m2/g、平均粒子径が6000μmの大阪ガスケミカル株式会社製の活性炭白鷺を、次亜担持粉末と同量の3g混合した以外は実施例2と同様にして鮮度保持剤を作成した。
Example 3
Using the BELSORP-mini manufactured by Microtrack Bell Co., Ltd. as the hypoxia-supported carrier of Example 2, the average pore diameter measured by nitrogen adsorption was 22 Å, the specific surface area was 923 m 2 / g, and the average particle diameter was 6000 μm. A freshness-preserving agent was prepared in the same manner as in Example 2 except that 3 g of activated carbon white cocoon manufactured by Osaka Gas Chemical Co., Ltd. was mixed with 3 g of the same amount as the hypoxia-supported powder.
次いで、デシケーターに、上記鮮度保持剤6gと、10gの苺を5個を入れ、室温で14日間放置した。14日後のデシケーター内のエチレンは検出されず、熟成も実施例2よりも進まず、カビの発生もなかった。しかも、塩素臭は全く無かった。 Next, 6 g of the freshness-keeping agent and 5 pieces of 10 g of cocoon were added to a desiccator and left at room temperature for 14 days. Ethylene in the desiccator after 14 days was not detected, ripening did not proceed more than in Example 2, and no mold was generated. Moreover, there was no chlorine odor.
実施例4
鮮度保持剤を、縦8cm、横8cmの通気性シート(トクヤマ製、NFRシート(商品名))に入れて周囲を熱融着した袋に入れデシケーターに設置した以外は実施例2と同様に行った。デシケーターに苺を入れ室温で14日間放置した。14日後のデシケーター内のエチレンは検出されず、熟成もほとんど進まず、カビの発生もなかった。また、塩素臭は、殆ど無かった。
Example 4
The same procedure as in Example 2 was performed except that the freshness-preserving agent was placed in a 8 cm long and 8 cm wide air-permeable sheet (manufactured by Tokuyama, NFR sheet (trade name)) and placed in a desiccator in a heat-sealed bag. It was. A desiccator was placed in a bowl and left at room temperature for 14 days. Ethylene in the desiccator after 14 days was not detected, ripening hardly progressed, and no mold was generated. Moreover, there was almost no chlorine smell.
実施例5
鮮度保持剤を縦8cm、横8cmの通気性シート(トクヤマ製、ラミポーラム(商品名))に入れて周囲を熱融着した袋に入れデシケーターに設置した以外は実施例2と同様に行った。デシケーターに苺を入れ室温で14日間放置した。14日後のデシケーター内のエチレンは検出されず、熟成もほとんど進まず、カビの発生もなかった。また、塩素臭は、殆ど無かった。
Example 5
The same procedure as in Example 2 was performed except that the freshness-keeping agent was placed in a breathable sheet (product of Tokuyama, Ramipolum (trade name)) 8 cm long and 8 cm wide, placed in a bag heat-sealed around and placed in a desiccator. A desiccator was placed in a bowl and left at room temperature for 14 days. Ethylene in the desiccator after 14 days was not detected, ripening hardly progressed, and no mold was generated. Moreover, there was almost no chlorine smell.
実施例6〜8
実施例1において、使用する多孔質シリカ粉末の種類、次亜塩素酸水溶液の有効塩素量、及び該多孔質シリカ粉末の全細孔容積に対する担持量を表1に示すように代えて次亜担持粉末よりなる鮮度保持剤を製造し、実施例1と同様な鮮度保持試験を行った。結果を表2に示す。
Examples 6-8
In Example 1, the kind of porous silica powder to be used, the amount of effective chlorine in the aqueous hypochlorous acid solution, and the amount supported on the total pore volume of the porous silica powder were changed as shown in Table 1, and hypochlorous acid supported. A freshness-keeping agent made of powder was produced, and the same freshness-keeping test as in Example 1 was performed. The results are shown in Table 2.
Claims (5)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016161347A JP2018027063A (en) | 2016-08-19 | 2016-08-19 | Freshness preservative of vegetable and fruit |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016161347A JP2018027063A (en) | 2016-08-19 | 2016-08-19 | Freshness preservative of vegetable and fruit |
Publications (1)
Publication Number | Publication Date |
---|---|
JP2018027063A true JP2018027063A (en) | 2018-02-22 |
Family
ID=61248150
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2016161347A Pending JP2018027063A (en) | 2016-08-19 | 2016-08-19 | Freshness preservative of vegetable and fruit |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2018027063A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110463754A (en) * | 2019-08-22 | 2019-11-19 | 中山市海枣椰农业科技有限公司 | A kind of biology composite slow release type antistaling agent and preparation method |
CN114957846A (en) * | 2022-05-31 | 2022-08-30 | 江阴诚公转印包装材料有限公司 | Fresh-keeping breathing film with double anti-fog performance and preparation method thereof |
-
2016
- 2016-08-19 JP JP2016161347A patent/JP2018027063A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110463754A (en) * | 2019-08-22 | 2019-11-19 | 中山市海枣椰农业科技有限公司 | A kind of biology composite slow release type antistaling agent and preparation method |
CN114957846A (en) * | 2022-05-31 | 2022-08-30 | 江阴诚公转印包装材料有限公司 | Fresh-keeping breathing film with double anti-fog performance and preparation method thereof |
CN114957846B (en) * | 2022-05-31 | 2023-11-28 | 江阴诚公转印包装材料有限公司 | Fresh-keeping breathing film with double anti-fog properties and preparation method thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3591515A (en) | Pulverulent chlorine dioxide compositions | |
JP4305664B2 (en) | Oxygen scavenger composition | |
JP5928458B2 (en) | Chlorine dioxide agent and method for generating chlorine dioxide | |
JP5218300B2 (en) | Food preservative and its package | |
EP0176371B1 (en) | Carbon dioxide sorbents for packaged foodstuffs | |
JP5605744B2 (en) | Stabilized chlorine dioxide agent and stable generation method of chlorine dioxide | |
JPH04215842A (en) | Oxygen absorbent | |
JPWO2012105457A1 (en) | Oxygen absorber and storage method thereof | |
JP2018027063A (en) | Freshness preservative of vegetable and fruit | |
EP0547761A1 (en) | Oxygen absorber and method for producing same | |
JP3200816U (en) | Freshness preservation material for fruits and vegetables | |
JP2003038143A (en) | Deoxidization agent composition | |
JP2003144113A (en) | Free-oxygen absorber | |
KR20200088000A (en) | Manufacturing method of wrapping paper using pulp with zeolite and bentonite added | |
KR20200093939A (en) | Manufacturing method of wrapping paper using pulp with charcoal, zeolite and bentonite added | |
KR101615003B1 (en) | Absorption agent of oxygen and producing process thereof | |
JP2008109856A (en) | Food quality retaining agent | |
JPH11207177A (en) | Deoxidizer | |
JPH03979B2 (en) | ||
JP6088940B2 (en) | Deoxidizer for alcohol-containing foods | |
JP2008229407A (en) | Oxygen absorbent | |
JP2013172683A (en) | Food quality retaining agent | |
JPS6117461B2 (en) | ||
JPS629376B2 (en) | ||
JP6420619B2 (en) | Ethanol vapor generating oxygen scavenger and food preservation method |