JPH11292722A - Method and apparatus for sterilization using vapor of isothiocyanic acid ester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide both a method for sterilizing various kinds of articles by using the vapor of an isothiocyanic acid ester (ISOTC) and an apparatus for sterilization using ISOTC. SOLUTION: An article packed with a material having vapor permeability of ISOTC is brought into contact with the vapor of ISOTC. The method comprises a process for introducing ISOTC in a vapor state or a fine particulate state of liquid clroplet into a sterilization chamber to form an atmosphere containing the vapor of ISOTC in the sterilization chamber, a process for sending the article to the sterilization chamber, a process for bringing the article into contact with an atmosphere gas containing ISOTC in the sterilization chamber to sterilize the article, a process for discharging the atmosphere gas in the sterilization chamber after the sterilization and a process for removing the vapor of ISOTC contained in the removed gas.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sterilization method using isothiocyanate vapor and an apparatus for performing sterilization using isothiocyanate.

[0002]

2. Description of the Related Art In various foods, glass products such as lenses, leather boots, leather jumpers, leather products such as fur coats, and products such as starch or cellulose paints and pastes.
Mold development has been observed, which significantly impairs high quality value or requires disposal. Even if there is no mold, the breeding of harmful microorganisms likewise significantly impairs the value of high quality products or requires disposal. For example, in foods and the like, problems such as fermentation and food poisoning due to multiplication of bacteria occur. Conventionally, in order to prevent the occurrence of mold on articles,
It is known that an article is hermetically packaged with a packaging material together with an oxygen scavenger to keep the oxygen concentration inside the package at 1% or less. In this method, although the occurrence of mold, which is an aerobic bacterium, can be effectively prevented, it cannot be an effective means for preventing the propagation of anaerobic bacteria causing food poisoning or fermentation. . It is also known that articles are hermetically packaged with a packaging material together with an ethanol generator in order to prevent the occurrence of mold and the propagation of general bacteria, so that the inside of the package is filled with ethanol vapor. However, in this method, the ethanol used is expensive, and a satisfactory effect cannot be obtained unless a relatively large amount of ethanol is used. Furthermore, although many antifungal agents and antibacterial agents are conventionally known, most of these chemical agents are toxic to the human body, so that their use is severely restricted. There is. Conventionally, antimicrobial activity (antimi
crobial Many natural products having an action are known, and in particular, wasabi is known to have an excellent bactericidal action. It is also known to sterilize food using isothiocyanate (hereinafter simply abbreviated as ISOTC), which is a main component of wasabi. For example, JP-A-57-99182 discloses that
An aqueous emulsion composition in which a solution of ISOTC dissolved in oil is emulsified and dispersed in water in the presence of an emulsifier is described. This aqueous emulsion composition is used by mixing it into food to sterilize the food. However, adding such aqueous emulsions to foods
ISOTC is not preferable because it impairs the flavor of the food and easily decomposes in the food. JP-A-58-63348 discloses a method for preserving fruits and vegetables by encapsulating a synthetic zeolite having a pore size of 5 to 10 ° and adsorbing ISOTC at a ratio of about 5% by weight together with the fruits and vegetables in a packaging container. Are listed. The zeolite adsorbed with ISOTC used here does not disperse an effective amount of vapor of ISOTC in the atmosphere. At a high humidity of 90% or more, the zeolite adsorbs moisture in the air and at the same time adsorbs zeolite. I was doing ISOT
C is emitted as vapor. However, in this known method, a synthetic zeolite having a pore size of 5 to 10 ° used as an adsorbent for ISOTC is very expensive, and the amount of adsorbed ISOTC is very low, about 5% by weight. including. Also, this known I
Synthetic zeolites that have adsorbed SOTC also have the disadvantage that they do not generate ISOTC vapor unless under high humidity. Therefore, such a synthetic zeolite adsorbing ISOTC cannot be effectively used as a general ISOTC steam generator. As described above, conventionally, several sterilization treatment techniques using ISOTC, which is a main component of wasabi, are known, but none of them can be satisfied from a practical viewpoint.

[0003]

The object of the present invention is to provide an IS
An object of the present invention is to provide a method for sterilizing various articles using steam of OTC, and an apparatus for performing sterilization using ISOTC.

[0004]

The present inventors have conducted various studies to solve the above-mentioned problems, and as a result, have found that the ISOTC
Is found to have high gas permeability to plastic films such as polyethylene film and polypropylene film, and by contacting articles sealed and packaged with such plastic films with ISOTC vapor, It has been found that sterilization can be performed effectively. According to the present invention, there is provided a method for sterilizing articles, wherein the article packaged with the vapor-permeable material of ISOTC is brought into contact with the vapor of ISOTC. Further, according to the present invention, the ISOTC
To form an atmosphere containing ISOTC vapor in the sterilization chamber, a step of charging an article into the sterilization chamber, and a step of charging the ISOTC in the sterilization chamber. A step of sterilizing by contacting with an atmosphere gas containing steam; a step of discharging the atmosphere gas in the sterilization chamber after the sterilization processing; and a step of removing ISOTC vapor contained in the discharged gas from the discharged gas. A method for sterilizing articles is provided. Still further, according to the present invention, there is provided a sterilization processing chamber including an introduction pipe for introducing ISOTC vapor into the processing chamber and a discharge pipe for discharging atmospheric gas in the processing chamber, and an ISOTC connected to the introduction pipe. And an apparatus for sterilizing articles, comprising: a storage container for accommodating the wastewater; and an ISOTC vapor removing device connected to the discharge pipe.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The bactericidal action referred to in the present invention means an antimicrobial action (antimicrobial action). actio
n) means germicidal action (germicida)
l action itself, as well as bacteriostatic action (germis)
static action).
In addition, bacteria (germ) include bacteria (bacteri).
a), fungi, spores, alga and other harmful microorganisms.

[0006] The ISOTC steam generator of the present invention is applied to various fields in which the propagation of harmful microorganisms is a problem, in addition to the food field, by utilizing the strong bactericidal action of the ISOTC steam generated therefrom. You. For example, in addition to preventing the occurrence of mold on food, it is also used to prevent the occurrence of mold that multiplies on various solid surfaces such as glass and concrete walls, and further prevents food spoilage and fermentation, resulting in deterioration of freshness. Used to prevent Further, it is used to deodorize or deodorize body odors such as axillary odor, sweat odor and foot odor by preventing bacterial decomposition of sweat and sebum. It is also used to treat skin sickness.

[0007] As used herein, the term "article" as used herein includes various products in which the propagation of harmful microorganisms such as food is problematic.

As the isothiocyanic acid ester (ISOTC) in the present invention, various aliphatic and aromatic isothiocyanic acid esters are used, and allyl isothiocyanate (CH ₂ ＣＨCHC) is preferred.
H ₂ NCS) and alkyl isothiocyanate (RNCS, R: alkyl group) are used. In the present invention, mustard oil can be used as it is.

Next, the present invention will be described in detail. (1) Preparation of oily liquid solution of ISOTC The vapor of ISOTC used in the present invention is ISOTC or ITC.
It can be released from the solution containing SOTC.
In this case, the ISOTC solution contains ISOTC in an oily liquid.
Is dissolved. As an oily liquid, temperature 3
A vapor pressure (saturated vapor pressure) at 0 ° C. of 2 mmHg or less, preferably 1 mmHg or less is used. In such a solution in which ISOTC is dissolved in an oily liquid having a low vapor pressure, the evaporation of ISOTC is remarkably suppressed, and the vapor released from the solution hardly contains the vapor of the oily liquid. Since it is substantially composed of
Even if the vapor is brought into contact with the article, no trouble occurs due to the vapor of the oily liquid. Generally, an oily liquid having a boiling point of 180 ° C. or higher, preferably 200 ° C. or higher, more preferably 220 ° C. or higher is advantageously used. As the oily liquid, for example, olive oil, sesame oil, safflower oil, soybean oil, camellia oil, corn oil, rapeseed oil, castor oil, sunflower oil, cottonseed oil, peanut oil, cocoa oil, palm oil, clove oil, coconut oil Oils and fats such as beef tallow, fish oil, hardened oil, turtle oil, egg yolk oil; waxes such as liquid lanolin; hydrocarbon oils such as liquid paraffin, liquid polyisobutylene and skrawan; high-grade oils such as oleic acid, linoleic acid and ricinoleic acid Fatty acid oils; higher alcohols such as octyl alcohol and oleyl alcohol; polyhydric alcohols such as polyethylene glycol, polypropylene glycol and glycerin; and ester oils such as linoleic acetate and hexyl laurate. The oily liquid used in the present invention is preferably odorless or almost odorless. ISOT for oily liquids
The dissolved amount of C was 0.01% in an oily liquid solution of ISOTC.
５０50% by weight, preferably 0.1-40% by weight.

[0010] ISOTC gives a strong pungent odor even in a small amount and is difficult to handle. However, by using the oily liquid solution as described above, the evaporation of ISOTC is effectively suppressed, and the ISOTC is easy to handle. It can be. Such an ISOTC solution can itself be used as an ISOTC steam generator. When dissolving ISOTC in an oily liquid, various auxiliary components can be added and dissolved as necessary. Examples of such auxiliary components include surfactants, high molecular substances, higher alcohols, higher fatty acids, fatty acid esters or fats and oils which are solid at room temperature, coloring agents, viscosity regulators, antioxidants and the like. It is also possible to add a small amount of a lower alcohol such as ethanol or propyl alcohol or a low boiling solvent such as acetone, methyl ethyl ketone, ether, ethyl acetate or hexane as an auxiliary component to control the amount of ISOTC evaporated from the oily liquid. it can.

The oily liquid containing ISOTC according to the present invention can be obtained by dispersing the seeds or cells containing ISOTC in the oily liquid as they are or in a pulverized state. The amount of seeds or cells dispersed in the oily liquid is 1 to 80% by weight, preferably 10 to 10% by weight in the oily liquid.
60% by weight. Such an oily liquid containing ISOTC can be used in a state containing its seeds or cells.

(2) Preparation of solid or gelled ISOTC vapor generating agent The ISOTC vapor is a porous substance (vapor generating) impregnated with the above-mentioned ISOTC oily liquid solution (hereinafter also simply referred to as ISTOC solution). Agent). When the porous material is impregnated and held by ISOTC itself, the evaporation rate of ISOTC is high,
When a porous material is impregnated with a large amount of ISOTC vapor, the working environment is deteriorated by the ISOTC vapor and the ISOT vapor impregnated and held in the porous material is generated.
The transpiration of C is still large, and it is difficult to stably maintain the porous material for a long period of time. According to the invention, such difficulties are overcome by impregnating and holding the porous material as a solution of the ISOTC in an oily liquid as described above. Although ISOTC easily reacts with moisture and has poor storage stability, the use of the above-described oily liquid solution solves this problem. As the porous substance, those generally used as an adsorbent, a filler or the like can be used. Such materials include clay or clay minerals such as diatomaceous earth, loess, clay, talc, zeolite, attapulgite, sepiolite, as well as activated carbon, silica, silica gel, alumina, magnesia, silica alumina, silica magnesia, synthetic aluminosilicate, etc. Is mentioned. As these porous substances, various shapes such as pellets, spheres, columns, cylinders, etc. can be used in addition to powders. In addition, it is desirable that the porous substance is a fired substance or a dried substance from which moisture is sufficiently removed. In order to impregnate and hold the solution in the porous material, a method of adding and mixing the ISOTC solution to the porous material, a method of spraying the ISOTC solution on the porous material, a method of immersing the porous material in the ISOTC solution, and the like. There is. I for porous materials
The impregnated retention ratio of the SOTC solution is equal to or less than the saturated absorption amount of the porous material, and usually 1 to 100 parts by weight of the porous material
The preferred content is appropriately determined according to the type of the ISOTC solution and the type of the porous substance.

In the present invention, when the porous material impregnated and held with the ISOTC solution is in the form of a powder, it is formed by a conventional molding method into various shapes such as a tablet, a sphere, a column, and a pellet. It can also be a molded article. In this case, a tableting method, an extrusion method, or the like is used as a molding method. When performing this molding, a molding aid is used. Examples of such a molding aid include carboxymethyl cellulose, polyvinyl alcohol, organic binders such as sodium alginate, bentonite, kaolin, alumina hydrogel, and silicate hydrogel. An inorganic binder is exemplified. Further, various short fibers such as gypsum whiskers can be used as a molding aid. Furthermore, the porous material containing these ISOTC solutions is used for controlling the ISOTC transpiration.
The surface of the porous material can be coated with a resin that transmits the vapor of ISOTC. With such a coating, the evaporation of ISOTC from the porous material can be further suppressed.

[0014] Another ISOTC steam generator according to the present invention can be obtained by encapsulating the ISOTC solution. As an encapsulation method in this case,
Conventionally known various methods are used. For example, the polymer solution from the outer nozzle and the I
There are a method of simultaneously ejecting the SOTC solution into the aqueous medium, an interfacial polymerization method, and the like. In addition, ISOTC solution or ISOT
The powdery porous material impregnated with the C solution exhibits a solid state at room temperature and has a melting point of 100 ° C or lower, preferably 40 to 60 ° C.
After adding to and mixing with the melt of the heat-fusible substance in the range described above, the mixture can be cooled, solidified, and pulverized to obtain an encapsulated product. In this case, examples of the heat-fusible substance include higher alcohols or esters thereof, higher fatty acids or esters thereof, oils and fats, and various waxes. Furthermore, a powdery porous material obtained by impregnating an ISOTC solution or an ISOTC solution into a melt of a curable resin composition (epoxy resin composition, unsaturated polyester resin composition, etc.) that is liquid at room temperature or at a temperature of 100 ° C. or lower. After adding and mixing the active substance, the mixture can be cooled and solidified, and then pulverized to form an encapsulated product. Further, an inclusion compound forming agent such as cyclodextrin or urea may be reacted with an ISOTC solution to form an encapsulated compound in the form of an inclusion compound.

In the present invention, the above-mentioned ISOTC solution, a product obtained by impregnating and holding a porous material with an ISOTC solution, a molded product of a porous material containing an ISOTC solution, and an encapsulated product of an ISOTC solution are sealed and packaged with a packaging material. And can be used. As the packaging material, a material that is at least partially permeable to ISOTC vapor is used. Examples of such packaging materials include films, sheets, containers, and the like formed of plastics that are permeable to ISOTC vapor such as polypropylene, polyethylene, and ethylene / vinyl acetate copolymer. Even a packaging material formed of a plastic that does not allow the permeation of the ISOTC vapor can be used as a packaging material that allows the permeation of the ISOTC vapor by perforating the material with a laser beam or the like. In addition, paper, non-woven fabric, those obtained by processing the surface of such paper or non-woven fabric, paper, non-woven fabric, cloth-like material laminated with a plastic film having permeability to vapor of ISOTC are used.

Still another ISOTC vapor generating agent according to the present invention can be obtained by incorporating the above-mentioned ISOTC solution into a gel-like substance. As the gel substance, various conventionally known substances are used. Such materials include agar, carrageenan, gelatin, carboxymethyl cellulose, glue, alginic acid, polyvinyl alcohol, dextrin and the like. As a method of including an ISOTC solution in a gel-like substance, in addition to a method of mixing and dispersing an ISOTC solution into a gel-like substance generated in advance, an ISOTC solution may be used as a raw material for producing a gel-like substance, particularly, a raw material for producing the gel-like substance. And the like. The content of ISOTC in the gel substance is usually 0.0
It is 5 to 20% by weight, preferably 0.5 to 10% by weight. The specific content of ISOTC is appropriately determined according to the purpose of use of the gel-like substance. When the ISOTC solution is contained in the gel substance, the ISOTC solution can be used in advance as a microencapsulated material. The gel-form ISOTC steam generating agent according to the present invention is usually used by being filled and packaged in a paper bag, a plastic film bag or a container obtained by subjecting the steam generating agent to water / oil repellency. In this case, a plastic film bag or container that can transmit the vapor of ISOTC is used.

The solution obtained by dissolving the ISOTC according to the present invention in an oily liquid having a vapor pressure at 30 ° C. of 2 mmHg or less is very easy to handle because the transpiration of the ISOTC is remarkably suppressed. . Moreover,
In this ISOTC solution, the ISOTC can be gradually evaporated over a long period of time.
C is also excellent in terms of the sustainability of the steam generation effect. Therefore, such a solution can be used by itself as an ISOTC
Can be used as a steam generator. Further, the porous material impregnated and held with the ISOTC solution or the IS
In the encapsulated product of the OTC solution, the transpiration of ISOTC is further suppressed. IS according to the present invention
In the gel-like substance containing the OTC solution, the volatility of ISOTC is remarkably suppressed, and the ISOTC is gradually released over a long period of time.

(3) Method and Apparatus for Sterilization Treatment According to the method for sterilization treatment of articles according to the present invention, the packaged articles are
Contacting with TC vapor. The concentration of the ISOTC vapor in contact with the packaging article in the total gas is typically 100
-5000 ppm, preferably 200-1000 ppm
It may be determined appropriately according to the packaging article. The contact time depends on the concentration of ISOTC in the gas.
0.1 to 6 when the vapor concentration of C is 100 ppm or more.
The time is 0 minute, preferably 0.5 to 30 minutes, and may be appropriately determined according to the target article.

In the present invention, the packaging article to be brought into contact with the vapor of ISOTC is polyethylene, polypropylene,
It is packaged with a plastic packaging material such as an ethylene / vinyl acetate copolymer. According to the study of the present inventors, it has been found that the vapor of ISOTC has a high gas permeability for the plastic packaging material as described above, and the article packaged with such a packaging material has a property that after the sterilization treatment, , Without secondary contamination by harmful bacteria,
It has been found that as long as the package is maintained, the article can be effectively protected from the effects of harmful bacteria. The gas concentration of the vapor of ISOTC brought into contact with the packaged articles is preferably higher than the concentration when processing unpackaged articles, and is usually 100 to 5000 ppm. Packaging materials for packaging articles are widely interpreted, and include containers of various shapes in addition to films and sheets. The preferred method of packaging an article according to the present invention is, for example, a method of housing and packaging an article in a bag, a method of placing an article in an open container such as a tray, sealing the opening with a film, and an article. A method of putting the whole in a container such as a tray and wrapping the whole film, a method of putting the article in a box body and wrapping the whole film, and a method of putting a liquid article in a plastic container and sealing it with a lid are exemplified. .

The term "packaging of articles" in the present invention includes a form of packaging that can prevent the articles from being contaminated by harmful microorganisms, and such that the articles inside the package are completely shielded from the outside air. It does not mean only complete sealing.

At least a part of the packaging material used for packaging the article is permeable to ISOTC vapor. Such packaging materials include polypropylene, polyethylene, ethylene / vinyl acetate copolymer,
Examples include films, sheets, containers, and the like formed of plastics having a permeability to ISOTC vapor such as an ethylene / propylene copolymer. Materials that do not transmit vapor of ISOTC (aluminum foil, nylon, etc.)
Can be used as a packaging material that allows the vapor of ISOTC to permeate by perforating microholes with a laser beam or the like.
Other packaging materials used for the packaging of articles include paper, non-woven fabric or those obtained by processing the surface of such paper or non-woven fabric, or paper, non-woven fabric, and cloth formed by laminating a plastic film that is permeable to ISOTC vapor. Objects and the like.

To carry out the sterilization process according to the invention, the packaged article is brought into contact with a gas containing ISOTC vapor.
As a method for this, there is a method in which the package is put in an airtight chamber and ISOTC is introduced into the airtight chamber as vapor or sprayed in a liquid state. In addition, the package is placed in an airtight chamber in which the vapor of ISOTC is present in advance. After a certain period of time,
There is a method to take this out. As a simple method, there is a method of putting a packaged article in a large-sized plastic bag, and further spraying ISOTC into the inside of the bag or adding a steam generating agent of ISOTC.

In order to generate ISOTC vapor,
In addition to the ISOTC itself, an ISOTC solution as described above or various solid substances containing the ISOTC solution can be used. ISOTC vapors are gradually released in a controlled amount from the ISOTC solution and solid substances containing it. The packaged article is then transferred to I
When processed by contact with SOTC vapor, I
SOTC vapor invades, and the invading ISOTC
After the sterilization treatment is completed, the vapor passes through the packaging material and gradually diffuses to the outside. From the viewpoint of the sterilizing effect on the articles, it is preferable that the concentration of the ISOTC vapor inside the package is high and the existence time is as long as possible.
Generally, inside the package, the steam of ISOTC is
Preferably, it is present at a concentration of 10 ppm or more for 10 minutes or more. Also, the vapor concentration of ISOTC inside the package gradually decreases over time because the vapor of ISOTC is gradually diffused to the outside. Can be controlled by enclosing an adsorbent in advance. That is, when the adsorbent is enclosed in a package in advance, the packaged article is subjected to ISOTC.
In the process of contacting with the steam of
The TC vapor is adsorbed and held, and after the treatment, the adsorbed ISOTC vapor is released, so that the vapor concentration of ISOTC in the package and the holding time of the vapor concentration can be controlled. ISOTC in packaging
It is not preferable that the vapor exists in the package for a long period of time because the vapor excessively migrates into the article and causes problems such as impairing the properties of the article. In general, select the type of packaging material and the amount of adsorbent, etc.
It is preferable to design so that the vapor concentration of C is 10 ppm or less.

[0024] In the package of the article obtained by the above-mentioned sterilization treatment, the vapor of the ISOTC inside the package is gradually released to the outside over time, and the package is distributed and sold. Since the package almost disappears, when the package is opened, a strong irritating odor of ISOTC is not felt.

According to the preferred method for sterilizing packaged articles according to the present invention, a step of introducing ISOTC in the form of vapor or droplets into the sterilizing chamber to form an atmosphere containing ISOTC vapor in the sterilizing chamber; Loading an article into the sterilization chamber, contacting the article with an atmosphere gas containing the ISOTC vapor in the sterilization chamber, and sterilizing the article. A method for sterilizing articles is provided, which comprises a step of discharging gas and a step of removing ISOTC vapor contained in the discharged gas. Further, according to the present invention, a sterilization processing chamber having an introduction pipe for introducing ISOTC into the processing chamber and a discharge pipe for discharging atmospheric gas in the processing chamber, and an ISOTC connected to the introduction pipe
And an ISOTC connected to the discharge pipe
An apparatus for sterilizing articles provided with the above-mentioned steam removing device.

Hereinafter, the sterilization method and apparatus will be described in detail. In this method and apparatus, a sterilization processing chamber (hereinafter, simply referred to as a processing chamber) is used. The sterilization chamber may have a space in which a required article can be inserted, and may be hermetically sealed so that the internal gas does not flow out. This sterilization chamber contains IS
An introduction pipe for introducing the OTC in a vapor state or a droplet fine particle form, and a discharge pipe for discharging the atmospheric gas in the processing chamber to the outside are separately provided. In addition, the structure of the processing chamber is set to an appropriate structure depending on whether the sterilization of the article is performed by a continuous method or a batch method. When the process is performed in a continuous manner, an inlet and an outlet for articles are provided in the processing chamber, and a conveyor circulating between the inlet and the outlet is provided. In this case, the inlet and the outlet have a hermetic structure to prevent the atmospheric gas in the processing chamber from flowing out, and only when the article enters at the inlet and when the article exits at the outlet. It has a structure that opens to
The inlet and outlet of such a hermetic structure can be constituted by conventionally known means. For example, an airtight structure can be obtained by partitioning the entrance and the exit in the processing chamber using a curtain made of a synthetic rubber sheet, a plastic sheet, or the like. On the other hand, in the case where the sterilization processing of the articles is performed in a batch system, a closed door for intermittently putting in and out the articles is provided in the processing chamber. In addition, I
A storage container for accommodating ISOTC in a vapor, liquid or solid state is connected to the SOTC introduction pipe via a mixer, a heater, or the like, if necessary. Is supplied in the form of fine droplets or vapor.

In the method for sterilizing articles according to the present invention, the step (A) of charging the articles into the sterilizing chamber described above includes the steps of:
OTC is introduced in the form of vapor or fine particles of droplets, and is introduced into the processing chamber
Step (B) of forming an atmosphere containing SOTC vapor is included. When the sterilization process is performed in a continuous mode, IS
Step (A) of introducing OTC is performed first, and then step (B) of introducing an article into the processing chamber is performed. On the other hand, when performing the sterilization process by a batch method, the step (B) of charging the articles into the processing chamber is performed first, and then the step (A) of introducing the ISOTC is performed. ISOTC introduces ISOTC in a vapor state or droplet fine particle form from a storage container into a processing chamber through an introduction pipe. If introduced in vapor form, use IS
OTC is vaporized in advance to form a gas containing ISOTC. On the other hand, when introducing in the form of fine droplets, ISOT
C is ejected into the processing chamber together with the gas through the mixing nozzle. Examples of the gas include air, nitrogen gas, carbon dioxide gas, and the like. ISOTC is vaporized, ISOTC
As a method for forming a gas containing steam, a liquid IS
A method of mixing a vapor formed by heating the OTC or its solution with a gas, a method of generating an ISOTC vapor from an ISOTC vapor generator, and mixing this with a gas,
There is a method in which a gas is passed through the liquid of C, and vapor of ISOTC is entrained in the gas. ISOT contained in gas
The vapor concentration of C is 5 ppm or more, the upper limit of which is an amount corresponding to the saturated vapor pressure in the gas, and generally 10 to 10 ppm.
5000 ppm. Using an ejector, I
When suction-mixing SOTC or its solution, use ISO
A gas containing TC vapor and droplet fine particles is obtained, and introducing this gas into the processing chamber is also an effective method.

The method for sterilizing an article includes a step (C) of bringing the article into contact with an atmospheric gas containing ISOTC vapor in the processing chamber. In this case, the processing temperature is generally 0 to 100 ° C., usually 20 to 60 ° C., although it depends on the type of the article. In the case of fresh food, the processing temperature is at room temperature or about 0 to 15 ° C. Low temperatures are employed. The processing pressure is not particularly limited, and reduced pressure or increased pressure is adopted, and it is preferably normal pressure or reduced pressure. When the sterilization process is performed in a continuous manner, in order to prevent the outflow of the atmospheric gas when opening and closing the inlet and outlet of the processing chamber, a pressure reduction of about −5 mm to −50 mm is particularly adopted in a water column. Is preferred. The atmosphere gas in the processing chamber is extracted from one place in the processing chamber and introduced into another place, or a fan is installed so that the ISOTC vapor becomes uniform as a whole. It is preferable to stir the atmosphere gas in the processing chamber evenly by rotating or the like.

In the above sterilization method, after the sterilization of the articles in the processing chamber is completed, a step (D) of discharging the atmosphere gas in the processing chamber and a step of removing the ISOTC vapor contained in the discharged gas ( E). Atmospheric gas can be discharged from the processing chamber by a suction pump, and removal of ISOTC vapor from the discharged gas can be performed using a device such as a cooler or an adsorption tower. As a cooler, the temperature of the gas is lower than the temperature of the
In particular, any structure can be used as long as it can be cooled to a temperature around 0 ° C. As the adsorption tower, a column filled with a gas adsorbent such as activated carbon, sepiolite, silica, and alumina is used. In order to completely remove the vapor of ISOTC from the gas, it is an effective method to combine a cooler and an adsorption tower.

Next, the present invention will be described in more detail with reference to the drawings. FIG. 1 is a view for explaining an embodiment of sterilization treatment of an article. FIG. 2 is a system diagram of an apparatus for performing a sterilization treatment of an article. In FIG. 1, 1, 4 are blowers and 2 is ISOT.
C is a steam generating chamber, 3 is a sterilization chamber, and 5 is an ISOTC vapor adsorption device. The ISOTC steam generation chamber 2 has a structure that accommodates the ISOTC therein. in this case,
ISOTC can be present in the form of a solution or a gel, or can be present in a state of being impregnated in a porous material. The form is not particularly limited as long as it can generate ISOTC vapor. The ISOTC vapor adsorption device 5 has an adsorbent therein and adsorbs and removes the ISOTC vapor contained in the introduced gas. As the adsorbent, generally, activated carbon, sepiolite, diatomaceous earth, alumina, silica,
Silica gel, silica / alumina, magnesia, zeolite, and the like are used, and any material having an adsorption effect on ISOTC vapor can be used.
In order to sterilize the articles, the blower 1 is operated, and the gas is passed through the steam generating chamber 2 through the line 6 and is subjected to the ISO.
A gas containing TC vapor is extracted through a line 10, and the gas is discharged from the sterilization chamber 3 containing the articles.
Introduce within. Air is usually used as a gas for conveying the ISOTC vapor, but may be nitrogen gas or carbon dioxide gas. By recirculating a part of the gas discharged from the ISOTC vapor generation chamber 2 to the line 9 through the line 11 and the valve 12, the vapor concentration of the ISOTC in the gas passing through the line 10 can be adjusted. The required concentration of ISOTC in the gas in the sterilization chamber 3
When the steam is mixed, the blower 1 is stopped and the valve 13 is closed to keep the sterilization chamber closed. This state is maintained for a certain period of time, and
C adsorption treatment is performed. It is preferable that a fan be provided in the sterilization chamber 3 to make the air in the room flow and promote the diffusion of the ISOTC vapor in the room. The vapor concentration of ISOTC in the sterilization chamber is 5 to 50 on a volume basis.
00 ppm (v / v), preferably 10 to 2000 pp
m (v / v). The processing time is a time during which a sufficient sterilizing effect of the article can be obtained, varies depending on the type of the article and the vapor concentration of ISOTC in the sterilizing chamber, and cannot be determined uniquely, but is generally 1 to 60 minutes, Preferably 5 to 2
A short time of 0 minutes is sufficient.

After the sterilization process is completed, the valve 15 is opened and the blower 4 is operated to discharge the gas in the sterilization chamber from the line 22 to the atmosphere via the adsorption device 5. In this case, in order to avoid decompression of the processing chamber,
It is preferable that a separate valve be attached to the sterilization chamber and this valve be opened to the atmosphere. In the adsorption device 5, ISOTC vapor contained in the gas is adsorbed and removed by the action of the adsorbent contained therein. The contact time of the gas in the adsorption device may be a time period in which the adsorption and removal can be sufficiently achieved.
A part of the gas extracted from the
Can be adjusted by recirculating to the line 17 through. The sterilization chamber 3 and the adsorption device 5 can be provided with a heating mechanism and a cooling mechanism to control the temperature. Further, in the adsorption device, when the adsorbent reaches saturated adsorption, a heating medium such as steam can flow through the adsorbent for regeneration.

In the present invention, the mixing of the ISOTC into the gas in the sterilization chamber is performed by spraying the ISOTC directly into the gas in a liquid or solution state without depending on the mixing of the ISOTC vaporized in the steam generating chamber. It can also be performed by evaporating inside. Separation and removal of ISOTC from the gas can also be performed chemically, using a substance having chemical reactivity with ISOTC, such as a solid amine, without using an adsorbent. As the sterilization chamber 3, any chamber having a closed structure can be used. Further, the gas containing the ISOTC vapor may be continuously introduced into the sterilization processing chamber 3 without being intermittently introduced as described above, and may be continuously extracted through the line 14. . In this case, a part of the gas extracted from the line 14 can be recirculated to the processing chamber 3 via the flow valve. The sterilization processing of the articles in the sterilization processing chamber 3 can be performed by a continuous method or a batch method.
In the case of using a continuous method, the article may be passed through the sterilization chamber 3 at a constant speed.

In FIG. 2, reference numeral 1 denotes a sterilization chamber, and 2 denotes
SOTC steam generation chamber, 3 blower, 4 gas distributor,
Reference numeral 5 denotes an ISOTC adsorption device. Sterilization chamber 1 and ISO
A pipe 6 having an on-off valve 7 is connected to the TC steam generation chamber 2, and a pipe 11 having an on-off valve 12 is connected between the sterilization chamber 1 and the blower 3. The blower 3 and the gas distributor 4 are connected by a pipe 14 having an open / close valve 15. As the gas distributor, for example, a gas pipe having a structure in which a gas inlet pipe and a gas exhaust pipe are attached to a large-diameter pipe sealed at both ends (header pipe) or the like can be used. Gas distributor 4 and ISO
A pipe 1 having an opening / closing valve 17 between the pipe 1 and the TC adsorption device 5
6 are connected. The gas distributor 4 and the ISOTC steam generation chamber 2 are connected by a pipe 18 having an on-off valve 19. The gas distributor 4 and the sterilization chamber 1 are connected by a pipe 20 having an on-off valve 21. Furthermore, a pipe 24 having a gas flow control valve 25 is connected between the downstream side and the upstream side of the blower so that the amount of gas transferred by the blower 3 can be controlled. The operation of each open / close valve can be electrically operated by a control panel.

In order to sterilize articles by using the above-mentioned apparatus, first, the opening and closing door 10 of the sterilization chamber 1 is opened, a required article is put in the inside, and the door 10 is sealed. Next, the valve 9, the valve 17, and the valve 21 are closed, and the valve 7, the valve 12, the valve 15, and the valve 19 are opened, and the blower 3 is operated. By operation of this blower 3,
Atmospheric gas (air) in the sterilization chamber 1 is fluidized, and continuously circulates through a circulation system formed by the blower 3, the gas distributor 4, the ISOTC steam generation chamber 2 and the sterilization chamber 1.
By this gas circulation, the vapor of the ISOTC vaporized in the ISOTC vapor generation chamber 2 is introduced into the sterilization chamber 1 along with the circulating gas, and the vapor concentration of the ISOTC in the sterilization chamber increases with time. When the vapor concentration of the ISOTC reaches a predetermined value, the valve 21 is opened, the valves 7 and 19 are closed, and the ISO
A gas containing TC vapor is circulated without passing through the ISOTC vapor generation chamber. The detection of the ISOTC vapor concentration in the gas can be performed by attaching a concentration meter to the sterilization chamber 1 or the pipe 11. In this case, a conventionally known type such as a gas chromatography type or an electric conductivity measurement type can be used as the densitometer. Next, after a lapse of a predetermined time, the valve 17 is opened and the valve 9 is opened, while the valves 19 and 21 are closed. This valve opening / closing operation can be automatically performed by a timer.
As a result, the purge gas is introduced from the pipe 8 into the sterilization chamber 1. Air may be used as the purge gas, but it is preferable to use sterilized air or nitrogen gas. After passing through the sterilization chamber 1, the purge gas is extracted from the pipe 11, passes through the blower 3 and the gas distributor 4, is introduced into the ISOTC adsorption device 5, where the IS contained in the gas is contained.
OTC vapor is adsorbed and removed. The gas from which the ISOTC vapor has been removed is extracted as exhaust gas by the pipe 30 and released to the atmosphere. When the concentration of the ISOTC vapor in the exhaust gas decreases to a predetermined value, the blower 3 is stopped, and the door 10 is opened to take out the sterilized article inside. In this manner, the sterilization operation ends. By repeating the above operation, the sterilization treatment of the article can be further continued.

FIG. 2 shows a batch-type processing apparatus. However, by using a sterilization processing chamber having a structure capable of continuously taking in and out of articles, the processing apparatus can be applied as a continuous-type processing apparatus. it can. The basic operation in this case is the same as above, except that a fixed concentration of I
It is necessary to continuously supply a gas containing SOTC vapor. For this purpose, the gas distributor 4 and the sterilization chamber 1 are connected by a pipe 20 having an open / close valve 21 having a gas flow control function as shown in FIG. A part of the air may be introduced into the sterilization chamber through this pipe, and the ratio of the gas flow through the pipe 20 to the gas flow through the pipe 18 may be controlled. According to the above-mentioned sterilization treatment, various articles including foods can be sterilized at low cost and safely and efficiently. In this case, I
After the sterilization process, the gas containing SOTC vapor is sent to the ISOTC adsorption device together with the purge gas, where
Since OTC is released to the atmosphere after being adsorbed and removed,
The user does not feel the strong irritating odor at the time of working, and the working environment is prevented from deteriorating.

[0036]

Next, the sterilizing effect of the ISOTC vapor generating agent used in the present invention and the ISOTC vapor evaporated therefrom will be described, and examples of the present invention will be described. The parts and percentages shown below are based on weight unless otherwise specified.

Reference Example 1 Allyl isothiocyanate was dissolved in edible oil (soy oil) as an oily liquid to obtain an ISOTC solution. Next, with respect to this solution, the degree of evaporation of the allyl isothiocyanate over time was sensory tested. In this test, 5 g of the ISOTC solution was placed in a petri dish (dimensions: diameter 75 mm, height 20 mm), and the strength of the odor evaporated from the petri dish at normal temperature was determined according to the following evaluation criteria. Table 1 shows the results. ◎: Irritating odor is visible. ○: Smell of pepper. △: Smell of pepper. ×: No odor. For comparison, add 0.05 g of allyl isothiocyanate to a Petri dish of the same dimensions as above. When the test was carried out, an irritating odor was observed over 30 minutes and disappeared at the first hour.

[0038]

[Table 1]

REFERENCE EXAMPLE 2 Allyl isothiocyanate was dissolved in corn oil at various concentrations, and about 9 g of this ISOTC solution was placed in a petri dish having a diameter of 85 mm (bottom area: 56.7 cm ² ) and a height of 15 mm. Closed system thermostat (volume 88
In 1), the change over time in the amount of evaporation of allyl isothiocyanate was examined. Table 2 shows the results. The evaporation amount of allyl isothiocyanate shown in Table 2 is the evaporation part by weight of allyl isothiocyanate per 100 parts by weight of the solution present in the petri dish at the start of the measurement.

[0040]

[Table 2]

Reference Example 3 40 parts of an ISOTC solution obtained by dissolving allyl isothiocyanate at a concentration of 50% in corn oil was impregnated into 100 parts of granulated calcined diatomaceous earth (diameter: about 1 mm, length: about 3.5 mm). Thus, an ISOTC steam generating agent was prepared, and using this, a time-dependent change in the amount of ISOTC steam was examined in the same manner as in Example 2. Table 3 shows the results. The amount of evaporation shown in Table 3 indicates the amount of I present in the petri dish at the start of the measurement.
It is an evaporation part by weight of allyl isothiocyanate with respect to 100 parts by weight of a steam generating agent of SOTC.

[0042]

[Table 3]

REFERENCE EXAMPLE 4 Allyl isothiocyanate was converted to 50 (v / v)%, 20 (v
/ V)%, 10 (v / v)% and 5 (v / v)% dissolved in corn oil to form a solution, and the vapor generated from this solution is passed through the enclosed space to mold fungi to be tested. (Room temperature), and then incubated at 28 ° C. for 3 days to examine the growth of mold. The results are shown in Table-4. The test target fungi are JIS Z 2911-1981, a strain designated by the "mold resistance test method"; Penicillium funiculosum Funiculo
sum Thom IFO 6345, blue mold) (indicated as bacterial species A in Table-4), cadmium globosum (Chaetomiun) globosum Ku
nze ex Fries IFO 6347, genus Ketomium) (indicated as bacterial species B in Table 4), gladosporium cladosporioides (Cladospo)
rium cladosporiolides (Fre
senius) de vries IFO 6348
(FERMS-8; IAM F517), Aspergillus sp. (Shown as fungal species C in Table 4). In addition, all of the above three types of fungi were 5
15 minutes with steam from a 0 (v / v)% ISOTC solution 12 minutes with steam from a 5 (v / v)% ISOTC solution
He was completely killed by the 0 minute exposure.

[0044]

[Table 4]

REFERENCE EXAMPLE 5 Dried fish (horse mackerel) was placed in one of the 3-litter containers, and the other was dried fish (horse mackerel) in addition to allyl isothiocyanate.
10 cc of a 10% soybean oil solution is placed in a container, stored in an open state, and each is covered. At room temperature, the dried fish was taken out from time to time, and the odor was examined. As a result, the dried fish stored with the allyl isothiocyanate solution was 6
Even on the day, the unique rawness of the dried fish was maintained and the freshness of the dried fish was good, but on the other hand, in the case of storing only dried fish,
A rotten smell was felt and its freshness was poor.

Reference Example 6 A test was conducted in the same manner as in Example 5 except that cutlets were used instead of dried fish. As a result, in the case where only the rice cake was stored, mold was generated on the third day, but in the case where it was stored together with the allyl isothiocyanate solution, no generation of mold was observed even in the first month.

Reference Example 7 30 parts by weight of pepper seeds were added to and mixed with 70 parts by weight of edible oil (soy oil). This operation could be easily carried out without deteriorating the working environment because the pepper seeds hardly produce the pungent odor of isothiocyanate.
Next, with respect to this ISOTC solution, the volatilization degree with respect to the elapsed time of the allyl isothiocyanate was functionally tested. In this case, the test was performed by adding a 20 g ISOTC solution to a Petri dish (dimensions: 70 mm in diameter, 15 m in height).
m), and at room temperature, the intensity of the odor volatilizing from the petri dish was determined according to the following evaluation criteria. The results are shown in Table-5. ◎… Irritating odor ○ ○ Spicy odor △… Spicy odor ×… No odor

[0048]

[Table 5] For comparison, 0.05 g of allyl isothiocyanate was placed in a petri dish having the same dimensions as above, and a similar test was conducted. As a result, an irritating odor was observed over 30 minutes, and after 1 hour, it did not smell at all. .

Reference Example 8 Allyl isothiocyanate was dissolved in a commercially available edible oil (soy oil) to obtain a solution having a concentration of 1 to 10%. This IS
10 parts of the OTC solution was uniformly mixed and dispersed in 100 parts of a carrageenan gel obtained from 5% of carrageenan and 95% of water to obtain a gel containing allyl isothiocyanate. Next, with respect to this gel-like material, the volatilization degree of the allyl isothiocyanate with respect to the elapsed time was examined functionally. In this case, the test was performed by dispensing 5 g of a gel-like substance into a Petri dish (dimensions: diameter 75 mm, height 20 m).
m), and the intensity of the odor volatilized from the petri dish at normal temperature was determined according to the following evaluation criteria. The results are shown in Table-6. ◎: Irritating odor is visible. ○: Smell of pepper. △: Smell of pepper. ×: No odor. For comparison, add 0.05 g of allyl isothiocyanate to a Petri dish of the same dimensions as above. When the test was carried out, an irritating odor was observed over 30 minutes and disappeared at the first hour.

[0050]

[Table 6]

Reference Example 9 Sample No. of Example 8 10 g of the gel-like substance of No. 4 was placed in a beaker, and this was placed in a commercially available hermetically sealed transparent plastic container (dimensions: 150 mm in length, 200 mm in width, 150 mm in height). And sealed and left at room temperature. For comparison, an experiment was performed in the same manner as described above except that no gel-like substance was used. As a result of the preservation test of the stiffness, mold generation was observed on the third day after storage in the comparative test using no gel-like substance of the present invention, but the test using the gel-like substance of the present invention for 30 days No mold was found on the surface of the rice cake even after storage.
This indicates that the gel-like substance of the present invention has excellent fungicide resistance, excellent bactericidal properties, and excellent freshness retention properties.

Reference Example 10 An experiment was conducted in the same manner as in Reference Example 9, except that bread was used instead of cut rice cake. As a result, in the comparative test not using the gel substance of the present invention, the occurrence of mold was observed on the third day after storage, whereas in the test using the gel substance of the present invention, mold generation was observed even after storage for 30 days. No outbreaks were seen.

Example 1 (1) Preparation of Sample A loaf of bread was cut to a thickness of 1 cm, and two sets of samples A and B were prepared. Group A: Three pieces of polyethylene bags each having a thickness of 100 μm, each of which is filled with bread and sealed by heat sealing. Group B: Bread is put into three 100 μm thick polyethylene bags one by one, degassed, and sealed by heat fusion. The three bags are placed in a closed container having an internal volume of about 2 liters. Approximately 5 cc of allyl isothiocyanate is held at 25 ° C. in this closed container so that it can be filled with volatilized allyl isothiocyanate. The enclosed bags of bread hold each in this for one hour.

(2) Experimental Results A total of six bags, each of the three sets A and B, were allowed to stand at room temperature, and it was observed whether abnormalities occurred in the packed bread. The results are shown in Table-7.

[0055]

[Table 7](Note)- : No mold generation + : 1 or 2 mold generation ++ : 3-4 molds generated +++: 5 or more molds or circular molds with a diameter of 1 cm or more
The spread of bi Living

Example 2 A commercially available batch-type compact vacuum drying apparatus having a drying chamber inside, an exhaust port and an outside air inlet on the wall, and a closed door was prepared. A vacuum pump is connected through an adsorbent filled with activated carbon in the mouth, and sepiolite powder (ISOTC steam generator) impregnated with allyl isothiocyanate is filled in the outside air inlet, and the vessel wall is ISO with gas exhaust pipe
The exhaust pipe of the TC storage container was connected via a three-way opening / closing valve to produce a sterilization apparatus of the present invention. Next, the door of this device was opened, and the towel was sealed and packaged in a polyethylene bag. After that, the door was closed, the three-way valve was opened, and the ISOTC in the ISOTC storage container was opened. The steam was diffused into the drying chamber of the device. In this state 2
After leaving for 4 hours, while driving the vacuum pump,
After closing the ISOTC storage container side of the three-way opening / closing valve and opening the outside air side, the atmospheric gas in the drying chamber is discharged while removing the ISOTC vapor contained therein by the adsorption tower, and then the vacuum pump is stopped. did. Next, open the drying room door,
The packaging glue was taken out and left as it was in the air. On the other hand, for comparison, the cut pieces were similarly hermetically sealed in a polyethylene bag and left in the air without sterilization. Mold generation was observed on the third day after leaving the mold for comparison, whereas no mold generation was observed on the rice paste sterilized by the present invention even when left for one month.

[0057]

According to the sterilizing method and the sterilizing apparatus of the present invention, various articles can be efficiently and effectively sterilized.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram of a sterilization process of an article.

FIG. 2 shows a system diagram of an apparatus for performing a sterilization treatment of an article.

[Explanation of symbols]

In FIG. 1, reference numerals 1 and 4 denote a blower, 2 an ISOTC vapor generation chamber, 3 a sterilization treatment chamber, and 5 an ISOTC vapor adsorption device. In FIG. 2, 1 is a sterilization processing chamber, 2 is an ISO
TC vapor generation chamber, 3 is a blower, 4 is a gas distributor, 5 is an ISOTC adsorption device.

Continued on the front page (31) Priority claim number Japanese Patent Application No. 1-88277 (32) Priority date Hei 1 (1989) April 7, (33) Priority claim country Japan (JP) (31) Priority claim number Special No. Hei 1-137792 (32) Priority Date Hei 1 (1989) May 30 (33) Countries claiming priority Japan (JP) (31) No. of priority claim Japanese Patent Application No. 1-239554 (32) Priority Date Hei 1 (1989) September 14, (33) Countries claiming priority Japan (JP)

Claims (5)

[Claims] 1. A method for sterilizing an article, comprising: bringing an article pre-packaged with a packaging material permeable to isothiocyanate vapor into contact with a gas containing isothiocyanate vapor. 2. A step of introducing isothiocyanate in the form of vapor or droplets into the sterilization chamber to form an atmosphere containing isothiocyanate vapor in the sterilization chamber, and mounting an article in the sterilization chamber. And a step of contacting the article with an atmosphere gas containing the vapor of the isothiocyanate in the sterilization chamber to perform a sterilization process; and, after the sterilization process, discharging an atmosphere gas in the sterilization chamber. Removing the vapor of isothiocyanate contained in the discharged gas from the discharged gas. 3. The method of claim 1, wherein said article is pre-packaged with a packaging material permeable to the vapor of isothiocyanate. 4. A sterilization chamber having an introduction pipe for introducing isothiocyanate into the processing chamber and a discharge pipe for discharging atmospheric gas in the processing chamber, and containing an isothiocyanate connected to the introduction pipe. Storage containers,
An apparatus for sterilizing articles, comprising a vapor removing device for isothiocyanate ester connected to the discharge pipe. 5. A sterilization chamber, an isothiocyanate vapor generation chamber connected to the sterilization chamber via an on-off valve, a blower connected to the sterilization chamber via an on-off valve, and an opening and closing with the blower. A gas distributor connected via a valve, an isothiocyanate vapor adsorption device connected to the gas distributor via an on-off valve, and an open / close connection between the gas distributor and the isothiocyanate vapor generation chamber A pipe provided with a valve, a pipe provided with an opening / closing valve connecting the upstream side of the blower and the steam generating chamber of the isothiocyanate ester, and a purge gas introduction pipe provided with an opening / closing valve connected to the sterilization chamber. An apparatus for sterilizing articles, comprising: