JPH11116226A - Dry ice containing allyl isothiocyanate and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain dry ice which suppresses the development and breeding of mold even in the case of a small residual amt. or after dissipation, produces sterilizing, antibacterial and antimold effects to a commodity and its vicinity in an open system or under conditions close to those of the open system, has the same effects even to the interior of a vessel used in low temp. preservation or distribution and is safe even when it is used for perishables, cake, etc. SOLUTION: Liquefied gaseous CO2 contg. dissolved allyl isothiocyanate (AIT) is converted into dry ice snow and compression-molded or dry ice snow made from liquefied gaseous CO2 is blended with at least one selected from among powder, a granular body and a liq. each carrying AIT and the blend is compression-molded to produce the objective dry ice contg. AIT.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to dry ice containing allyl isothiocyanate (hereinafter referred to as AIT) having a bactericidal, antibacterial and fungicidal action, and a method for producing the same. The freshness of products, especially fresh foods, confectionery, etc.
The present invention relates to dry ice and a method for producing the same, which can more effectively prevent rot and deterioration.

[0002]

2. Description of the Related Art The low-temperature preservation methods which have been implemented so far are various, but in view of simplicity and cost, a method using ice, a cold preservative, and dry ice is generally used. Although ice is inexpensive, it does not reach 0 ° C. or lower, and water remains after the ice is thawed, which often damages the product, and breeding of fungi and fungi tends to occur. Since the cooling agent has a longer cooling time than ice, its use frequency has been rapidly increasing in recent years. However, there is a problem in disposal treatment, resources are wasted, and re-use is troublesome in re-freezing. is necessary. Further, similarly to ice, the temperature rises after the cooling time has passed, and it becomes easy for bacteria and mold to multiply on the product. Dry ice is most suitable for keeping cool at 0 ° C or less, only carbon dioxide remains after sublimation, and has the advantage of not directly damaging the product, but after a long time, dry ice becomes a small amount and finally disappears, Like ice and cold storage, it loses its ability to maintain low temperatures, which increases the temperature of the product and makes it easier for the product to grow bacteria and mold.

[0003] Therefore, conventionally, when using dry ice, for example, in order to prevent the product temperature from rising, a large amount of dry ice is put in a sealed container in consideration of the time required for maintaining low temperature. However, due to an unexpected situation or the like, the dry ice disappears before the required low-temperature maintenance time elapses, or the low-temperature required time is greatly extended from the initially set required time, so that the low-temperature maintenance cannot be performed.

[0004] In summer, spraying a freshness preservative or a synthetic preservative may be performed to maintain the quality of the product.
Many of these are chemicals and are never welcome in terms of their safety to the human body.

[0005] Furthermore, even if the product is removed from the container, after the dry ice disappears, the temperature rise in the container and the presence of moisture make it easy for bacteria and mold to multiply, so the container must be carefully re-used before use. It is necessary to perform cleaning and the like.

[0006]

Thus, the appearance of dry ice having the following characteristics is desired. Even after the remaining amount of dry ice is reduced or disappeared, dry ice with little bacteria, mold, etc., with little proliferation, in an open system or close to this, sterilization, antibacterial and antibacterial, including around the product Moldy dry ice,
Dry ice that has a sterilizing, antibacterial, and antifungal effect even in containers that have been used for low-temperature storage and distribution, and dry ice that is safe to use for fresh foods, fresh confectionery, etc.

Accordingly, an object of the present invention is to provide a dry ice having the above characteristics. Also,
Another object of the present invention is to provide a method for producing dry ice as described above.

[0008]

The above object is achieved by the following invention. (1) Dry ice containing AIT. (2) At least a portion has an AIT-containing portion (1)
Dry ice as described. (3) The dry ice according to (1) or (2), wherein the AIT is carried on a carrier and contained in the dry ice. (4) The dry ice according to (3), wherein the support is in the form of a powder, granule or liquid at room temperature in the embodiment supporting AIT. (5) AIT characterized in that liquefied carbon dioxide gas in which AIT is dissolved is converted into dry ice snow and then compression molded.
And a method for producing dry ice. (6) Dry ice snow made of liquefied carbon dioxide
A method for producing dry ice containing AIT, comprising blending at least one selected from a powder, a granule and a liquid carrying IT, followed by compression molding.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION AIT, which is a main component of essential oils such as wasabi and mustard, has been recognized as a food additive, and has been known to have a strong sterilizing, antibacterial, and antifungal effect especially in the gaseous state. I have. Its MIC (minimum inhibitory concentration)
Is 10 ppm for mold and yeast, 15 ppm for gram-negative bacteria, and 30 pp for gram-positive bacteria.
m and has a strong effect.

The AIT used in the present invention may be a natural product or a synthetic product, and can be appropriately selected depending on the use. Furthermore, an AIT-containing composition may be used instead of AIT 100%. That is, for example, it may be an essential oil containing AIT, a crude extract from wasabi or mustard, or a crudely purified product. It is desirable to use natural products when utilizing foods such as fresh foods.

The amount of AIT in the dry ice of the present invention is 0.001 to 5% by weight, preferably 0.005 to 0.5% by weight in the dry ice containing AIT. AI
If the amount of T is less than 0.001% by weight, the antibacterial effect tends to be significantly reduced, while if it exceeds 5% by weight, dry ice and AIT tend to violently sublime and sublimate in the air.

The dry ice having an AIT-containing portion in at least a part of the present invention means that the AIT-containing dry ice exists in the AIT-free dry ice. Preferably, the AIT-containing portion is located at the center of the dry ice so that the AIT appears after the remaining amount of the dry ice is reduced. Specific examples include those in which AIT-containing dry ice is sandwiched between AIT-free dry ice and those in which AIT-containing dry ice is surrounded by AIT-free dry ice.

The powders, granules and liquids carrying AIT are those in which AIT is carried on a carrier as described below.

The carrier used for the powder carrying AIT includes monosaccharides such as glucose, galactose and fructose; disaccharides such as maltose, lactose and sucrose; starch;
Examples include powders of polysaccharides such as dextrin and cellulose derivatives such as cellulose, methylcellulose and ethylcellulose.

The amount of AIT is preferably in the range of 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the powder carrying AIT.

As a method of supporting AIT on the powder carrier, a method described in, for example, JP-A-6-192018 can be used. Specifically, a closed stirring mixer, a V-type mixer or a fluid mixer is used. By a mixer such as a layer mixer,
The AIT can be supported by adding AIT little by little while stirring the powder as the support and uniformly spreading the AIT on the support. In preparing the powder carrying AIT, a surfactant may be added as necessary. As the surfactant, a nonionic surfactant is preferable, and examples thereof include sorbitan fatty acid ester, glycerin fatty acid ester, sucrose fatty acid ester, polyglycerin fatty acid ester, and polyoxyethylene sorbitan fatty acid ester. Specifically, sorbitan monolaurate, sorbitan monocaprate, glyceryl monostearate, sucrose stearic acid monoester, sucrose palmitic acid monoester, sucrose oleic acid monoester, decaglyceryl diisostearate, decaglyceryl monoester Laurate, hexaglyceryl monolaurate, hexaglyceryl monomyristate, polyoxyethylene sorbitan monoisostearate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan trioleate, and the like. The amount of the surfactant to be added is usually 0.01 to 20 parts by weight, preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the powder as the carrier.
It is in the range of 1 to 10 parts by weight, more preferably 1 to 5 parts by weight.

Examples of the carrier used for the granules supporting AIT include granules such as porous particles such as silica gel, cellulose, acetylated chitin, polyethylene, polyurethane and polypropylene. AIT is preferably supported in the range of 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the granules supporting AIT. A is attached to the granule carrier.
As a method for supporting the IT, a method known per se can be used, and for example, the IT can be supported by operating in the same manner as the powder carrier. Specifically, AIT or a mixture of AIT and the nonionic surfactant is dissolved in highly volatile alcohols such as methanol and ethanol, and the solution is dissolved in a granulator containing granules, a coating machine or a fluidized bed. After uniformly spraying the granules inside, the granules supporting AIT can be obtained by drying to remove alcohols. Further, AIT or a mixture of AIT and the nonionic surfactant is dissolved in the above-mentioned alcohols, and the granules are immersed in the solution and then dried to obtain an AI.
Granules carrying T can also be obtained.

The carrier used for the liquid carrying AIT may be a liquid carrier that does not dissolve AIT or a liquid carrier that dissolves AIT. That is, the liquid carrying the AIT may be, for example, an emulsion or a solution. AIT is preferably carried in the range of 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, per 100 parts by weight of the liquid carrying AIT.

The emulsion carrying AIT is preferably an aqueous solution in oil (O / W type) in which a core oil in which AIT is dissolved is added with an appropriate emulsifier and dispersed in water. -47272 can be obtained. Examples of the core oil include natural oils such as soybean oil, coconut oil, corn oil, and palm oil, and medium-chain fatty acid triglycerides (eg, Panassate 800, 810, 87 manufactured by NOF Corporation).
5) Synthetic oils such as higher fatty acid triglycerides which are oily at room temperature (eg, triglyceride oleate, triglyceride isostearate). Examples of the emulsifier include sucrose fatty acid esters such as sucrose stearate, sucrose palmitate and sucrose oleate, and phospholipids such as lecithin. The amount of the core oil in the emulsion is usually 1 to 30% by weight, preferably 5 to 30% by weight in the emulsion carrying AIT.
It is in the range of 20% by weight.

The solution carrying AIT is a solution in which AIT is dissolved in a solvent. The solvent can dissolve AIT,
There is no particular limitation as long as the solvent is inactive or very slow in reacting with AIT. Examples of such a solvent include the above-mentioned natural oils, synthetic oils, alcohols such as methanol, ethanol, propanol, and isopropanol.

The dry ice containing AIT of the present invention can be produced by, for example, a method of blending AIT with dry ice snow made of liquefied carbon dioxide gas and then compression molding. Dry ice, dry ice in which AIT is uniformly dispersed, From the viewpoint of producing dry ice in which agglomerate oil droplets of AIT do not remain after disappearance, it is preferable to produce by the following method. A method in which liquefied carbon dioxide gas in which AIT is dissolved is converted into dry ice snow and then compression molded. A method in which at least one selected from powders, granules and liquids carrying AIT is blended into dry ice snow made of liquefied carbon dioxide gas and then compression molded.

The above method or the above method is more specifically as follows. Is a production method in which liquefied carbon dioxide gas in which AIT is dissolved is sprayed to form dry ice snow, which is put into, for example, a press die of a dry ice press and compression-molded. Here, the liquefied carbon dioxide gas in which AIT is dissolved can be obtained by, for example, putting AIT in a high-pressure resistant cylinder, sealing the liquefied carbon dioxide gas, and uniformly dissolving AIT. Dry ice snow can be obtained by rapidly discharging the liquefied carbon dioxide gas in which AIT is dissolved as described above into the air from the nozzle of the high-pressure cylinder. The liquefied carbon dioxide gas in which AIT is dissolved is
If necessary, for example, when lowering the AIT concentration, it may be further diluted with liquefied carbon dioxide gas. The degree of dilution is usually up to about 1000 times. The dilution is performed, for example, industrially, in front of a liquefied carbon dioxide gas outlet, by quantitatively mixing two kinds of gases, that is, liquefied carbon dioxide gas in which AIT is dissolved and liquefied carbon dioxide gas for dilution, and Can be carried out by generating dry ice snow from the powder, shaping it, and compressing and solidifying it. Alternatively, dry ice snow containing AIT and dry ice snow not containing AIT may be mixed and diluted. The content of AIT is preferably in the range of 0.0003 to 2% by weight, more preferably 0.002 to 0.2% by weight, in the liquefied carbon dioxide gas in which the AIT has been dissolved.
It is.

[0023] Dry ice snow is sprayed with liquefied carbon dioxide gas, and at least one selected from powders, granules and liquids carrying AIT is blended into the dry ice snow, which is then put into, for example, a press die of a dry ice press. This is a manufacturing method by compression molding. Specifically, for example, in the case of a powder or a granule carrying AIT, the powder or the granule may be added to dry ice snow as it is, uniformly mixed with a normal powder mixer, and then compression-molded with a press. . In the case of a liquid carrying AIT, by spray-mixing with dry ice snow, fine droplets of the liquid are changed to fine solids by dry ice and become a mixture of solids, and the mixture is compressed by a press machine. What is necessary is just to shape | mold. Here, dry ice snow made of liquefied carbon dioxide is
Dry ice snow that does not substantially contain AIT. The method for producing dry ice snow made of liquefied carbon dioxide is the same as described above except that AIT is not used. In the case of dry ice produced by the method, the compounding amount of the powder, granules and liquid carrying AIT is 0.01 to 25 parts by weight with respect to 100 parts by weight of dry ice snow.
Preferably it is 0.05 to 5 parts by weight.

[0024]

EXAMPLES Hereinafter, the method for producing AIT-containing dry ice of the present invention will be specifically described with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. Here, the evaluation of the dispersibility of AIT was performed by finely crushing the formed AIT-containing dry ice, and then measuring the AIT content in the crushed material.

Example 1: Dry ice containing AIT-supported powder 10 parts by weight of AIT was added to 2 parts by weight of polyoxyethylene sorbitan trioleate and 88 parts by weight of maltose in a stirrer, and AIT was supported on maltose by stirring and mixing. Then, an AIT-supported powder was obtained. 1g of this powder
And 1 kg of dry ice snow were mixed, and the mixture was placed in a press die of a dry ice press and compression-molded to obtain dry ice containing AIT. AIT in the obtained dry ice
Was well dispersed (AIT concentration 0.01
%).

Example 2 Dry Ice Containing AIT-Supported Powder An AIT-containing dry ice was prepared in the same manner as in Example 1 except that 1 g of the AIT-supported powder was changed to 5 g. AIT in the obtained dry ice was well dispersed (AIT concentration: 0.05%).

Example 3 10 parts by weight of dry ice AIT containing AIT-supported granules and 2 parts by weight of sorbitan monolaurate were added to 90 parts by weight of porous cellulose particles (Biscopearl manufactured by Rengo Co., Ltd.), and the mixture was stirred and mixed. And uniformly mixed to obtain AIT-supported granules. 1 g of these granules and 1 kg of dry ice snow were mixed, and A
IT-containing dry ice was obtained. AIT in the obtained dry ice was well dispersed (AIT concentration: 0.01%).

Example 4: 5 parts by weight of dry ice AIT containing an AIT-supported emulsion, 1 part by weight of purified coconut oil, 1 part by weight of lecithin, 1.2 parts by weight of sucrose oleate monoester were uniformly dispersed with a homogenizer and stirred. 91.8 parts by weight of purified water was added thereto, and the mixture was emulsified with a homomixer to obtain an AIT-supported emulsion. 2 ml of this emulsion was sprayed and mixed with 1 kg of dry ice snow to obtain AIT-containing dry ice in the same manner as in Example 1. AIT in the obtained dry ice was well dispersed (AIT concentration 0.01
%).

Example 5 Dry Ice Containing AIT-Supported Emulsion AIT-containing dry ice was prepared in the same manner as in Example 4 except that the amount of the AIT-supported emulsion was changed from 2 ml to 10 ml.
AIT in the obtained dry ice was well dispersed (AIT concentration: 0.05%).

Example 6: AIT containing 10 parts by weight of dry ice containing AIT carrying solution dissolved in 90 parts by weight of a solvent
A loading solution was obtained. Here, corn oil was used as a solvent.
1 ml of this AIT carrying solution is 1 kg of dry ice snow
The AIT-containing dry ice was obtained in the same manner as in Example 1 below. AIT in the obtained dry ice was well dispersed (AIT concentration 0.01
%).

Example 7 AIT dissolved liquefied carbon dioxide gas was obtained by dissolving 0.1 part by weight of dry ice AIT produced by direct spraying of liquefied carbon dioxide gas dissolved in 100 parts by weight of liquefied carbon dioxide gas. This AIT-dissolved liquefied carbon dioxide gas was directly sprayed to obtain dry ice snow, and AIT-containing dry ice was obtained in the same manner as in Example 1 below. AIT in the obtained dry ice was well dispersed (AIT concentration 0.30%).

Example 8: Dry ice manufactured by spraying after diluting liquefied carbon dioxide gas dissolved in AIT 1 part by weight of dry ice snow of Example 7 was mixed with 2 parts by weight of dry ice snow containing no AIT, and In the same manner as in Example 1, AIT-containing dry ice was obtained. AIT in the obtained dry ice was well dispersed (AIT concentration: 0.01%).

Example 9: Dry ice having an AIT-containing portion The AIT-containing dry ice obtained in Example 1 was placed on a dry ice snow layer, and further covered by being sandwiched between AIT-free dry ice snow and compressed. Dry ice having an AIT-containing dry ice layer in the middle was obtained by molding.

The following experiment was performed using the dry ice obtained in the above example. Here, the measurement of the AIT concentration is performed using a Kitagawa-type Wasauro detector tube (manufactured by Komei Rika Co., Ltd.).
This was performed using

EXPERIMENTAL EXAMPLE 1 Assuming a closed system, a styrene foam insulated box (inside: vertical x horizontal x height = 33.5 x 17.5 x 15.2)
780 g of the dry ice prepared in Example 1 was placed at a height of 7 cm in the center at a height of 2 cm at a midpoint between the center and the end (8.5 cm from the end) in the vertical direction.
A thermometer and an AIT measuring unit were installed at a position of 3 cm, and the temperature in the cool box, the AIT concentration, and the remaining amount of dry ice were measured with the lapse of time. Similarly, using 450 g of dry ice prepared in Example 4, 50 g of dry ice prepared in Example 7, and 580 g of dry ice prepared in Example 8, respectively, the temperature in the cool box, the AIT concentration and the remaining amount of dry ice Was measured. The results were as follows.

[0036]

[Table 1]

It is apparent from this that AIT is generated in a small amount at a low temperature and in a large amount with an increase in the temperature. A
The amount of IT release can be arbitrarily controlled by selecting the AIT concentration, the dosage form and the amount of the preparation.

Experimental Example 2 317 g of the dry ice prepared in Example 1 was placed in a KOP bag (vinylidene chloride-coated biaxially oriented polypropylene bag, 20 cm × 30 cm), and a partially open system was assumed.
Open a hole for degassing and leave it at room temperature.
The concentration was measured. Similarly, the dry ice 260 g prepared in Example 2 and the dry ice 2 prepared in Example 4
Using 80 g, 243 g of dry ice produced in Example 5, 262 g of dry ice produced in Example 7, and 248 g of dry ice produced in Example 8, the temperature in the bag and the AIT concentration were measured. The results were as follows.

[0039]

[Table 2]

It is apparent that AIT is generated in a very small amount at a low temperature and in a large amount with an increase in the temperature. Also, dry ice having various AIT release amounts can be obtained depending on the AIT concentration, dosage form, and the like. After the disappearance of dry ice, powder or granules remain in the case of AIT-carrying powder or granules containing dry ice, and liquid remains in the case of AIT-carrying emulsions or solution-containing dry ice. It can be easily discarded by washing with water. In particular, if AIT-supported powder or dry ice containing granules is placed in a microporous polyethylene bag or the like, the bag can be easily discarded. further,
Dry ice produced from AIT dissolved liquefied carbon dioxide is
Since it evaporates together with dry ice, disposal is not particularly necessary.

[0041]

The AIT-containing dry ice of the present invention generates a small amount of AIT at a low temperature and has a low activity of bacteria and mold, so that a sufficient antibacterial effect can be obtained. The generation of AIT increases as the temperature rises, and after the disappearance of dry ice, the AIT can provide sufficient sterilization, antibacterial and antifungal effects.
Therefore, the AIT-containing dry ice of the present invention maintains sterilization, antibacterial and antifungal effects even after the disappearance of dry ice, as well as in the presence of dry ice. It is effective for

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI A23L 3/358 A23L 3/358 (72) Inventor Yuichi Mizukami 1-47, Chuo, Joto-ku, Osaka-shi, Osaka Calex Co., Ltd. (72) Inventor Isao Mikami 1-16-7 Nishi-Shimbashi, Minato-ku, Tokyo Nippon Sanso Corporation (72) Inventor Naoko Takeuchi 1-16-7 Nishi-Shimbashi, Minato-ku, Tokyo Inside Nippon Sanso Corporation (72) Inventor Shoji Komai In the Alps, 4--11-14 Omori Minami, Ota-ku, Tokyo

Claims (6)

[Claims] 1. Dry ice containing allyl isothiocyanate. 2. The dry ice according to claim 1, which has at least a portion containing an allyl isothiocyanate-containing portion. 3. The dry ice according to claim 1, wherein the allyl isothiocyanate is carried on a carrier and contained in the dry ice. 4. The dry ice according to claim 3, wherein the carrier is in the form of a powder, granules or liquid at room temperature in an embodiment supporting allyl isothiocyanate. 5. A method for producing allyl isothiocyanate-containing dry ice, comprising forming dry ice snow from liquefied carbon dioxide gas in which allyl isothiocyanate is dissolved, and then compression molding. 6. An allyl isothiocyanate characterized in that dry ice snow made of liquefied carbon dioxide gas is mixed with at least one selected from powders, granules and liquids supporting allyl isothiocyanate, followed by compression molding. Dry ice production method.