JPH0690661A - Freshness-keeping material containing hinokitiol - Google Patents

Abstract

PURPOSE:To obtain a freshness-keeping material for vegetables, fruits, etc., having the preservation temperature selectable in a wide range by the selection of carrier and suitable for the preservation over a long period by supporting hinokitiol on vegetable powder and a hydrophilic resin such as a water-absorbing resin. CONSTITUTION:An ethanol solution of hinokitiol is added to a hydrophilic resin composed of a water-absorbing resin (e.g. crosslinked acrylic acid salt polymer, crosslinked copolymer of vinyl alcohol and acrylic acid salt and crosslinked product of polyvinyl alcohol grafted with maleic anhydride) and/or vegetable powder (e.g. chaff powder, wood flour and bamboo flour). After thoroughly mixing the components, the mixture is spread on a vat and ethanol is evaporated by blasting hot air of about 50 deg.C for 5min to the mixture. The hinokitiol is supported on the hydrophilic resin and/or the vegetable powder by this process. Since the supporting power of hinokitiol depends upon the kind of the carrier, the carrier is properly selected to get a desired preservation temperature and obtain the objective agent for keeping the freshness of vegetables, fruits, etc., and suitable for the preservation of the vegetables, etc., in a wide preservation temperature range over a long period.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a freshness-retaining material for fruits and vegetables. More specifically, the present invention relates to a freshness-keeping material for fruits and vegetables, which comprises a hinokitiol carried on a hydrophilic resin and / or a vegetable powder.

[0002]

2. Description of the Related Art As a freshness-keeping material for fruits and vegetables, it suppresses the growth of microorganisms and ripens,
Paper or non-woven fabric impregnated with hinokitiol, which has the effect of preventing aging, and adsorbed (Japanese Patent Publication No. 3-1942), zeolite or ceramic fine powder adsorbed into a film or coated on corrugated board (special (Kaihei 2-156876), those contained in a synthetic resin film (Japanese Patent Laid-Open No. 3-167261), etc.
It is already known.

All of the above-mentioned freshness-retaining materials using hinokitiol utilize the sublimability of hinokitiol, and the effect is exhibited when the packaging container is filled with hinokitiol. However, since the sublimability of hinokitiol is significantly affected by temperature, the conventional freshness-maintaining material described above has a problem that it is difficult to obtain the effect at a low temperature of 1 to 15 ° C. which is the freshness-keeping temperature of fruits and vegetables. In recent years, the distribution of fruits and vegetables tends to be expanded by a low-temperature distribution system called a so-called cold chain, but a freshness-retaining material using hinokitiol may not be able to exhibit a sufficient freshness-retaining effect in this low-temperature distribution system. In addition, recently, along with the simplification of eating habits, cut and processed vegetables called cut vegetables have been widely used, but the tissue of the vegetables has been damaged by cutting or the like. Therefore, browning and microbial propagation are likely to occur, and it is one of the things that it is difficult to maintain freshness even under low temperature storage. For these cut vegetables, the conventional freshness-retaining material using hinokitiol cannot obtain a sufficient effect, which is the reason why this kind of freshness-retaining material does not spread in the distribution field.

Further, at the terminal stage of distribution, 15 to 25 ° C.
Therefore, the conventional freshness-retaining material using hinokitiol has the following problems because it is exposed to relatively high temperature. That is, hinokitiol, paper, non-woven fabric,
In the case of a synthetic resin film impregnated or adsorbed into a sheet, the sublimation rate of hinokitiol is high, and it is not possible to support a large amount of hinokitiol in spite of its bulky volume. Although the effect of is obtained, there is a risk that the effect will not be sustained because hinokitiol sublimes rapidly.
As a solution to this problem, a method has been devised in which an inclusion compound such as cyclodextrin contains hinokitiol to give sustained release, but the inclusion compound is expensive and cannot be said to be a practical method. Further, in the method of using porous particles such as zeolite and ceramics as a carrier and the method of containing it in a synthetic resin film, it is possible to support a large amount of hinokitiol, but since the hinokitiol holding power of the carrier is large, the carrier particles or There is a problem that the sublimation speed from the film is slow and the freshness-keeping effect is difficult to be sufficiently expressed despite the amount of hinokitiol supported.

As described above, the conventional freshness-retaining materials using hinokitiol have difficulty in adjusting the sublimation rate with respect to temperature, and as a result, hinokitiol in the packaging container does not reach the effective concentration or the effective concentration. However, there is a problem in that it cannot be maintained for a long time. That is, the problem to be solved by the present invention is to provide a hinokitiol-containing freshness-retaining material capable of maintaining an effective concentration of hinokitiol in a container for a long period of time even under a wide range of storage temperatures ranging from low temperature to high temperature. It is in.

[0006]

[Means for Solving the Problems] In order to solve the above problems, the present inventors have studied a carrier for supporting hinokitiol. That is, when searching for carrier particles that accelerate the sublimation rate of hinokitiol even at a low temperature of 10 ° C. or lower, the sublimation rate of hinokitiol was found to be high when a water-absorbent resin used in paper diapers and the like was used as a carrier. It was found that a high product can be obtained even at a low temperature, and that a carrier having a moderately slow sublimation rate instead of being immediately sublimated at a relatively high temperature is also found to have a water-soluble resin such as polyethylene oxide and rice husks or wood. It was found that hinokitiol having a slow sublimation rate can be obtained by using plant powder such as flour as a carrier. Furthermore, it has been found that the use of hydrophilic resin such as water-absorbent resin and water-soluble resin, vegetable powder, etc. as a carrier can provide a freshness-retaining material having a humidity control effect in addition to the above effects. Was completed. That is, the gist of the present invention is a hinokitiol-containing freshness-retaining material obtained by supporting hinokitiol on a hydrophilic resin and / or vegetable powder.

The hinokitiol-containing freshness-retaining material of the present invention has a different ability to retain hinokitiol depending on the carrier used, and therefore, for example, when storing fruits and vegetables at a relatively low temperature (1 to 15 ° C.), it seems to be a water absorbent resin. In addition, a carrier with a fast sublimation rate of hinokitiol is used, and a carrier with a slow sublimation rate of hinokitiol such as water-soluble resin, rice husk and wood flour at relatively high temperature (15 to 25 ° C.) is used. Also, if the storage temperature varies, or if stored for a long period of time, these can be mixed, the effective concentration of hinokitiol in the packaging container can be maintained for a long period of time by using the compounding amount appropriately changed. Stabilization of the freshness preservation effect can be expected.

The hinokitiol used in the present invention is a known compound, which is extracted and purified from Taiwan cypress and Aomori Hiba, β-tsuyapurisin, 4-isopropyl-2-
Hydroxy-2,4,6-cycloheptatriene-1-
ON and the metal salts thereof.

Examples of the hydrophilic resin used in the present invention include water-absorbent resin and water-soluble resin. As the water-absorbent resin, it is usually used for applications such as paper diapers and water-retaining agents for soil improvement, which have a pure water absorption capacity (10-1000 gH ₂ O / g) of about 10 to 1000 times its own weight. If there is, it is not particularly limited. Specific examples thereof include crosslinked products of acrylate polymers, crosslinked products of vinyl alcohol-acrylate copolymers, crosslinked products of maleic anhydride grafted polyvinyl alcohol, acrylate-
Cross-linked methacrylic acid copolymer, cross-linked saponified methyl acrylate-vinyl acetate polymer, cross-linked starch-acrylic acid salt graft copolymer, hydrolyzed starch-acrylonitrile copolymer Examples thereof include crosslinked products, saponified products of starch-ethyl acrylate graft copolymers, and carboxymethylcellulose crosslinked products. Such a water-absorbent resin is already on the market, and in the present invention, it may be appropriately selected and used from the water-absorbent resins according to the application.

Examples of the water-soluble resin used in the present invention include methyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, polyethylene oxide and the like. Among them, when polyethylene oxide is used, since the resin has a relatively low melting point, it was molded by heating slightly and the resin was supported with hinokitiol, or sandwiched between paper, non-woven fabric, film and the like. In this case, the resin can be prevented from falling off, which is preferable. Polyethylene oxide has a weight average molecular weight of 20,000 to 1
Those in the range of 0,000,000 can be used.

Examples of the vegetable powder used in the present invention include common vegetable powders such as chaff powder, wood powder and bamboo powder. The method of finely pulverizing these vegetable powders is not limited in any way, but, for example, rice husk powder of rice grains is finely ground by crushing rice husk under high heat (for example, trade name "Sumiselco" ( (Commercially available from Sumitomo Seika)) is preferably used.

The particle size of these hydrophilic resins and vegetable powders used in the present invention is 1 to 2000 μm, preferably 1 to 1
It is preferably 000 μm. If the particle size is smaller than 1 μm, handling becomes difficult,
If it is larger than m, the surface area of the particulate matter becomes small and the amount of hinokitiol supported becomes small, which is disadvantageous. As a carrier, the above-mentioned hydrophilic resin and a granular substance such as vegetable powder,
In order to prepare the freshness-retaining material of the present invention, a simple method of dissolving hinokitiol in a solvent, adding and mixing the above-mentioned granular substance therein, and then removing the solvent by drying is adopted. The solvent for dissolving hinokitiol is not particularly limited, but one having a low boiling point is practically preferable. The amount of the hinokitiol used per unit weight of the granular substance and the effective period of the freshness-retaining material to be obtained are determined by the amount of the hinokitiol used, but usually, the hinokitiol is used in an organic solvent such as ethanol, ether or acetone. 0.1 to 10% by volume of the particulate matter is added to 1 volume of the solution, and the mixture is stirred with stirring, and then the solvent is removed with hot air or room temperature to obtain the desired hinokitiol-containing freshness. A holding material can be obtained. As a result, the hinokitiol content is usually 0.01 to 2
A freshness-keeping material of 0 mg / g is obtained. The obtained hinokitiol-containing freshness-retaining material may be used as it is by putting an appropriate amount in a commercially available tea pack or the like, but a kitchen kitchen towel for household use, a sheet that is sandwiched between cotton paper and various non-woven fabrics is used. Is also good.

[0013]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Example 1 10 g of a water-absorbent resin having a particle size of 100 to 500 μm (trade name: Aqua Keep 10 SH, pure water absorption capacity 800 g H ₂ O / g, Sumitomo Seika Chemicals Co., Ltd.) was placed in a 100 ml beaker while stirring with a stir bar. 15 ml of the ethanol solution (2.5 mg / ml) was added, thoroughly mixed and then spread on a vat, and warm air at about 50 ° C. was blown for about 5 minutes to vaporize the ethanol to obtain 10 g of a hinokitiol-supporting water-absorbent resin. . Hinokitiol content is 3.1
It was mg / g (freshness keeping material: A).

Example 2 100 ml of 10 g of chaff powder (trade name: "Sumiselco", manufactured by Sumitomo Seika Chemicals, Ltd.) having a particle size of 300 to 1000 μm
12 ml of an ether solution of hinokitiol (5 mg / ml) was added to a beaker with stirring with a stirring rod, and the ether was vaporized at room temperature while sufficiently mixing to obtain 10 g of hinokitiol-supported chaff powder. The hinokitiol content was 5.4 mg / g (freshness keeping material: B).

Example 3 In the same manner as in Example 2 except that 10 g of polyethylene oxide having a particle size of 100 to 1000 μm (trade name: PEO-18, average molecular weight: 4.5 million, manufactured by Sumitomo Seika Chemicals, Ltd.) was used. Hinokitiol-supported polyethylene oxide 10
g was obtained. The hinokitiol content was 5.4 mg / g (freshness retaining material: C).

Example 4 5 g of hinokitiol-supporting water-absorbent resin obtained in the same manner as in Example 1 and 5 g of hinokitiol-supporting chaff powder (freshness-keeping material: B) obtained in Example 2 were mixed to maintain freshness. A material was obtained (freshness maintaining material: D).

Comparative Example 1 Zeolite (trade name: Zeorum F-9, manufactured by Toso Corporation) 10 g
And hinokitiol ethanol solution (10mg / ml)
100 ml was thoroughly mixed and stirred in a beaker to sufficiently adsorb hinokitiol. Then, the unadsorbed hinokitiol was sufficiently washed with ethanol, spread on a vat and warm air was blown to evaporate the ethanol to obtain 10 g of hinokitiol-adsorbed zeolite. Hinokitiol content is 48 mg /
It was g (freshness keeping material: E).

Comparative Example 2 A commercially available freshness-retaining rayon paper supporting 210 mg / m ² of hinokitiol on rayon paper was used as a freshness-retaining material: F.

Test Example 1 Storage of Shiitake Mushroom Using the freshness-retaining material A obtained in Example 1, the freshness-retaining effect at 10 ° C. was observed. That is, the raw shiitake mushrooms (weight 25-
35 g, the umbrella was opened for 7 to 8 minutes, and 6 umbrellas having a diameter of 4 to 6 cm and no browning spots were placed on the umbrella. Next, in the first tray, the freshness-retaining material prepared in Example 1: A2 g (containing about 6 mg of hinokitiol) was put on a commercial tea pack (7 × 8 cm).
Put in a polyethylene bag (25 x 35c
m, thickness 20 μm). (Experimental zone No. 1).
As a control experiment, the second tray was prepared by placing 1 g of the freshness-retaining material E prepared in Comparative Example 1 in a commercially available tea pack and sealing it in a polyethylene bag (experimental section N).
o. 2). In addition, the third tray is a freshness-maintaining rayon paper of Comparative Example 2 10 × 31 cm (hinokitiol 6.5 mg).
(Included) and sealed in a polyethylene bag (experimental area N
o. 3). One polyethylene bag containing 6 fresh shiitake mushrooms was used as one unit, and three units were provided in one experimental section. The raw shiitake mushrooms in each polyethylene bag were stored for 10 days in a constant temperature bath at 10 ° C.
Ten days later, the polyethylene bag was opened, and the color change of the shiitake mushroom and the mold development state were visually observed to examine the discoloration rate (the rate at which brown discoloration spots are seen on the lump), the mold development rate, and the presence or absence of putrefactive odor. The results are shown in Table 1. The discoloration rate is calculated by the formula (I)
Therefore, the mold generation rate was calculated by the formula (II).

[0020]

[Table 1]

[0021]

[Equation 1]

Experimental section No. 1 using the freshness keeping material of the present invention
The shiitake mushroom of No. 1 is No. Compared with 2-3 shiitake mushrooms, the results were significantly better in terms of discoloration rate, mold generation rate, and presence or absence of odor.

Test Example 2 Storage of Matsutake Mushroom Using the freshness-retaining material: D obtained in Example 4, 2 to 25 ° C
The effect of keeping freshness was observed. That is, two Styrofoam containers (26 × 32 × 17 cm, volume 8.3)
Each liter of matsutake mushroom (opening the umbrella for 5-7 minutes, umbrella diameter 6
Ten umbrellas (no browning spots at 10 cm) were put in each. Then, in a first container, the freshness-retaining material obtained in Example 4:
A commercially available tea pack (7 × 8 cm) containing 2 g of D was put (experimental group No. 1). As a control experiment, the second
In the container of, the freshness maintaining rayon paper of Comparative Example 2 25 × 10
cm2 pieces (containing 21 mg of hinokitiol) covered the matsutake mushroom (experimental group No. 2). One unit of this styrofoam box was used as one unit, and one unit was provided with 3 units. Then, the cold storage agent was added to each Styrofoam container, and it sealed. These were placed in a thermostatic chamber at 25 ° C. and stored for 5 days. The temperature change in the Styrofoam container reached 2 ° C one day after the start of storage and reached 25 ° C on the second day. On the 5th day, the lid was opened and the color change of the pine mushrooms and the presence or absence of mold were visually observed, and the discoloration rate (the rate at which brown spots were seen on the lump), the mold incidence rate, and the presence or absence of off-flavor were examined. The results are shown in Table 2.

[0024]

[Table 2]

From this, the experimental zone N containing the freshness-keeping material D
o. The No. 1 matsutake mushroom is No. 1 in the experimental section. 2 to 25 ° C from No. 2 Matsutake
It can be seen that the freshness was significantly retained even under the temperature condition of.

Test Example 3 Storage of Strawberries Using the freshness-retaining material A obtained in Example 1, the freshness-retaining effect at 5 ° C. was observed. That is, 13 strawberries (size, L) collected on the day were placed in each of two strawberry packs. Next, the freshness-keeping material prepared in Example 1, A 4 g (containing 12 mg of hinokitiol) in a commercially available tea pack (7 × 8 cm) was added to the first pack (Experimental group No. 1). Also, as a control experiment,
Nothing was added to the second pack (Experimental No.
2). Each of these is a polyethylene bag (25 x 35c
m, thickness 20 μm) and sealed. This strawberry 13
One unit was set as a unit pack and 3 units were set for one experimental section.
These strawberries were stored at 5 ° C., and after 17 days, the hardness of the strawberries, the change in color and the presence or absence of mold were examined as indicators of freshness. Experimental section No. The surface of the strawberry No. 2 softened from around 10 days, and mold development was observed in some strawberries. The strawberry of No. 1 showed significantly good results after 17 days, which was not much different from the initial one, and the mold incidence was 0% even after 17 days.

Test Example 4 Storage of Mango Using the freshness-retaining material: C obtained in Example 3, the freshness-retaining effect at 20 ° C. was observed. That is, the inner diameter is 25c
Five mangoes from Okinawa, each of the same size and maturity, were placed in two m desiccators made of glass. afterwards,
For one desiccator, the freshness-retaining material obtained in Example 3, C:
What was put in a commercially available tea pack (7 × 8 cm) of 2 g was added (experimental group No. 1). Also, as a control experiment,
In the second desiccator, 15 × 40 cm of freshness-maintaining rayon paper of Comparative Example 2 was put (experimental section No. 2). One desiccator containing 5 mangoes was used as one unit, and one experimental section was provided with 3 units. These desiccators were stored at 20 ° C. When visually observing the daily change in the maturity of mango,
Experimental section No. In Example 2, the yellowness gradually increased, and after 2 weeks, the surface was softened and mold was observed in a part of the five mangoes. In No. 1, the yellow color gradually increased, but there was no softening of the surface even after 3 weeks, and no generation of mold was observed.

Test Example 5 Storage of cut cabbage Using the freshness-retaining material: A obtained in Example 1, the effect of keeping the cut cabbage at 5 ° C. was observed. That is, each of the two commercially available strawberry packs, the spring cabbage collected on the day was cut into 2 mm width with a food slicer.
00g was added. The first pack was a freshness-keeping material (A2 g) obtained in Example 1 placed in a commercially available tea pack (Experiment No. 1). As a control experiment, the second pack contained 10x31c of freshness-maintaining rayon paper of Comparative Example 2.
The cut cabbage was wrapped around with m (Experimental Zone No.
2). Each of these packs is a polyethylene bag (25 x 3
5 cm, thickness 20 μm) and sealed. Each pack contains 200g of cut cabbage as one unit
A unit is provided. Each pack containing 200 g of cut cabbage was stored at 5 ° C. After 5 days, the browning degree of the cut cabbage was visually observed. The cut cabbage of No. 1 is No. The degree of browning was significantly lower than that of the cut cabbage of No. 2.

[0029]

EFFECTS OF THE INVENTION The hinokitiol-supporting freshness-retaining material of the present invention has a different ability to retain hinokitiol depending on the carrier used, and therefore can be appropriately selected according to the storage temperature. Moreover, by mixing and using, it can be suitably used for storage temperature in a wide range and storage for a long period of time.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Naoyuki Hashimoto, Inventor, No. 1 Irifune-cho, Shikima-ku, Himeji City, Hyogo Prefecture, Sumitomo Seika Chemical Co., Ltd. 2nd Research Laboratory (72) Shoji Naito 1-13, 9th Dan, Chiyoda-ku, Tokyo No. 5 Sumitomo Seika Co., Ltd. Tokyo head office

Claims (6)

[Claims] 1. A hinokitiol-containing freshness-retaining material obtained by supporting hinokitiol on a hydrophilic resin and / or vegetable powder. 2. The hydrophilic resin is 10 to 1000 g H ₂ O.
The hinokitiol-containing freshness-retaining material according to claim 1, which is a water-absorbent resin having a pure water-absorption capacity of / g. 3. The hinokitiol-containing freshness-retaining material according to claim 1, wherein the hydrophilic resin is a water-soluble resin. 4. The hinokitiol-containing freshness-retaining material according to claim 3, wherein the water-soluble resin is polyethylene oxide. 5. The hinokitiol-containing freshness-retaining material according to claim 1, wherein the vegetable powder is rice husk powder, wood powder or bamboo powder. 6. The particle size of the hydrophilic resin and the vegetable powder is 1 to
The hinokitiol-containing freshness-retaining material according to claim 1, which has a thickness of 2000 μm.