JP2018027063A - Freshness preservative of vegetable and fruit - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a simple method that suppresses maturity and corruption caused during transportation of vegetables and fruits, and maintains the freshness of the vegetables and fruits.SOLUTION: Freshness preservatives are characterized by comprising hypochlorous acid water solution supported powder in which a hypochlorous acid water solution is supported to the porous silica powder having pores where the pore of a pore diameter of 70-1000 Å holds 80% or more and having an average particle diameter of 200-2000 μm at 80% or less of the total pore volume of the porous silica powder in a total pore volume, the total pore volume that is 0.3-2.5 cc/g, and so that the available chlorine may become 0.02-40 pts.mass to the porous silica powder of 100 pts.mass.SELECTED DRAWING: None

Description

  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.

  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.

  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.

  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).

  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.

  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.

  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.

  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.

Japanese Patent Laid-Open No. 2-131536 Japanese Patent Laid-Open No. 4-320641 JP 59-39243

  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.

  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.

  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.

  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.

  The porous silica powder to be used is preferably a gel method silica powder or a precipitation method silica powder.

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.

  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.

  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.

  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.

  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.

  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.

  Hereinafter, the method of the present invention will be described in detail.

  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.

  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.

  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.

  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.

  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.

  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.

  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.

  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%.

  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.

  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.

  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.

  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.

  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.

  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.

  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.

  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.

  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. .

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.

  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. .

  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.

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.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

  In the examples, each measured value was measured by the following method.

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) 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) 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) Average particle diameter of porous silica It measured using the laser diffraction scattering type particle size distribution apparatus LA-950V2 (brand name) by Horiba.

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).

  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.

  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.

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.

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.

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.

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.

  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.

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.

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.

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)

  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 accounting for 80% or more, and the average particle diameter is 200 to 2000 μm. A hypochlorous acid aqueous solution is added to the porous silica powder at 80% or less of the total pore volume of the porous silica powder, and the effective chlorine content is 0.02 to 100 parts by mass of the porous silica powder. A freshness-keeping agent comprising a hypochlorous acid aqueous solution-supported powder supported so as to be 40 parts by mass.   The freshness-keeping material according to claim 1, wherein the repose angle of the hypochlorous acid aqueous solution-supported powder is 60 degrees or less.   The freshness-keeping agent according to claim 1 or 2, wherein the porous silica powder is a gel method silica powder or a precipitation method silica powder. Activated carbon powder having an average pore diameter of 10 to 30 Å, a specific surface area of 700 to 1500 m ² / g, and an average particle diameter of 100 to 10000 μm is 0.1 to 500 parts per 100 parts by mass of the hypochlorous acid aqueous solution-supported powder. The freshness-keeping agent according to any one of claims 1 to 3, which is contained at a ratio of parts by mass.   The freshness-keeping agent according to any one of claims 1 to 4, which is filled in a breathable bag.